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Understanding stainless steelmaking through

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converting
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DOI: 10.1179/1743285511Y.0000000031

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Understanding stainless steelmaking through

computational thermodynamics: Part 3 AOD
converting
D. R. Swinbourne*1, T. S. Kho1, B. Blanpain2, S. Arnout3 and D. E. Langberg1
The major issue in stainless steelmaking is the difficulty of oxidising carbon from molten steel
without also oxidising large proportions of expensive chromium. This can, however, be achieved
by reducing the partial pressure of the gaseous product of carbon oxidation, carbon monoxide,
by dilution with argon. Modern stainless steelmaking is dominated by duplex processes which
prepare a high carbon melt in an electric arc furnace, and then decarburise it in an argonoxygen
decarburisation (AOD) converter. In this work, the thermodynamic basis of preferential carbon
oxidation by dilution of oxygen with argon is discussed, together with a review of AOD practice.
The AOD process was simulated using computational thermodynamics software to illustrate the
way in which it can achieve very low carbon levels in the molten steel bath without excessive cooxidation of chromium. The slag reduction stage using ferrosilicon additions was also modelled
and shown to be able to recover almost all oxidised chromium from the slag, limited only by the
accompanying increase in the silicon content of the steel. The models, although simple and easy
to develop, correctly predicted all trends in output variables as input parameters were changed
and often matched plant data very well. The models provide a valuable learning tool for those
interested in pyrometallurgical processing in general, and stainless steelmaking in particular.
Keywords: AOD, Stainless steel, Chromium, Decarburisation, Computational models

Introduction
Thermodynamic background
The difficulties faced in the production of stainless steels
have been discussed in previous papers (Kho et al., 2010;
Swinbourne et al., 2010). Stainless steels need to have
relatively high chromium contents but very low carbon
contents, typically y0?03 wt-%C. Carbon can be removed
by oxidation, but as carbon is oxidised to very low levels,
its activity drops rapidly, which makes chromium oxidation increasingly favourable. The need to oxidise carbon
without also oxidising much expensive chromium is the
main technical challenge in stainless steelmaking.
Dennis and Richardson (1953) described the competitive oxidation of carbon and chromium in molten
stainless steel according to the reaction
2Crz3CO(g)~Cr2 O3z3C, DG 0 at 16000 C~173 kJ (1)
where the thermodynamic data were taken from the HSC
Chemistry for Windows database (Roine, 1998). The

1
School of Civil, Environmental and Chemical Engineering, RMIT
University, Melbourne, Australia
2
Department of Metallurgy and Materials Engineering, Katholieke
Universiteit Leuven, Kasteelpark Arenberg 44, Leuven, Belgium
3
InsPyro NV, Kapeldreef 60, Leuven, Belgium

*Corresponding author, email drs@rmit.edu.au

2012 Institute of Materials, Minerals and Mining and The AusIMM

Published by Maney on behalf of the Institute and The AusIMM
Received 26 March 2011; accepted 22 September 2011
DOI 10.1179/1743285511Y.0000000031

effect of reducing the carbon monoxide partial pressure

on this equilibrium was examined using the Ellingham
diagram format in a previous paper (Swinbourne et al.,
2010). Figure 1 shows three lines representing carbon
oxidation for three carbon monoxide partial pressures
and at a carbon activity appropriate to 0?03 wt-%C. The
activity of Cr2O3 was taken by Dennis and Richardson to
be unity, while the activity of chromium in an 18 wt-%Cr
stainless steel was taken as 0?2; therefore, the chromium
oxidation reaction is represented by a single line. When
the carbon monoxide partial pressure is 100 kPa, reducing the carbon content to 0?03 wt-% without chromium
oxidation is only possible above y1940uC. At a carbon
monoxide partial pressure of 10 kPa, the required
temperature drops to y1610uC and at 1 kPa, it is only
y1370uC. Lowering the carbon monoxide partial pressure enables the necessary extent of decarburisation to
be achieved without chromium loss at much more
favourable temperatures, where refractory erosion is not
excessive.
Recognition by Krivsky (1973) of the benefits of
lowering the carbon monoxide partial pressure completely changed stainless steelmaking practice, which then
became duplex, i.e. an electric arc furnace (EAF)
provides a molten steel charge which is then decarburised in a converter in which the carbon monoxide
partial pressure can be reduced. The argonoxygen
decarburisation (AOD) process uses argon to dilute

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Stainless steelmaking through computational thermodynamics: Part 3

1 Ellingham diagram for carbon and chromium oxidation

reactions with variable carbon monoxide partial pressures as given

injected oxygen and was developed by Union Carbide

and commercialised at Joslyn Stainless Steel Company
in 1968, as described by Krivsky. Total pressure is
reduced in the vacuumoxygen decarburisation (VOD)
process, developed by Edelstahlwerk Witten in Germany
from 1962 to 1968 (Schmidt et al., 1968).
In this work, AOD converting will be reviewed, and
then modelled using computational thermodynamics to
obtain a better understanding of the changes taking
place in the molten steel bath during processing.

Argonoxygen decarburisation technology

The AOD process became the preferred method for
making stainless steel within 10 years of its development
(Klein et al., 1981) and today accounts for over 75% of
the worlds stainless steel output (Wei and Zhu, 2002a).
In comparison with the VOD process, it offers easier
maintenance and simpler deslagging capabilities, in that
the AOD converter can be tilted and has a spout;
whereas, the VOD ladle must be lifted out of the vessel
by crane and moved to a separate deslagging stand. The
economic production of a much wider range of alloy
steels including nickel based superalloys, cobalt based
alloys and super stainless steels containing .26 wt-%Cr
and ,0?02 wt-%C has been enabled by the advent of the
AOD process. The AOD process, however, does have
the disadvantage of consuming large quantities of
expensive argon. The ferrochromium industry also was
forced to shift from the production of expensive low
carbon grades to inexpensive low grade, high carbon
ferrochromium due to the dominance of the AOD
process (Klein et al., 1981).
The AOD converter has been described (Choulet, 1997)
as pear shaped and is a steel shell lined with refractories,
as shown in Fig. 2. The vessel sits in a trunnion ring which
enables it to be rotated for charging and tapping and also
facilitates rapid replacement of the vessel with a spare
rebricked converter when the refractories become excessively worn. The design of AOD converters and all
associated drive equipment and gas control facilities has
been described by Williams and Ludlam (1978).
The dimensions of a typical 50 t converter are given
by Moore and Marshall (1980). A large freeboard is

24

2 Diagrammatic AOD converter [modied from Scott (1976)]

necessary to contain splash when the converter is being

blown, the specific volume usually being 0?40?8 m3 t21
(Davis, 1994; Choulet, 1997). Mixing in the AOD is
excellent and there are no large stagnation zones (Fabritius
et al., 2003). Gas is injected through two to seven annular
tuyeres placed low on the side, with a total blowing rate
of 0?71?0 Nm3 min21 t21 (Moore and Marshall, 1980;
Wijk, 1992; Syvanen, 2006). Annular tuyeres have a
central pipe through which oxygen/argon flows, surrounded by an outer pipe through which argon flows at
y0?1 Nm3 min21 t21 (Wei and Zhu, 2002a) to provide
protection to the surrounding refractories. Low flowrates
through the tuyeres cause backflow of steel, blocked
tuyeres and uneven refractory wear while high flowrates
cause strong bath oscillations and severe splashing. The
number, diameter and angle of the tuyeres need to be
optimised, although this is difficult because gas flowrate
varies through the AOD cycle (Fabritius et al., 2003).
Most AOD converters now use mixed blowing
(Syvanen, 2006), i.e. top blowing oxygen lances are added
to side blowing converters. This increases converter
productivity and allows the AOD to match the increased
productivity of EAFs. Top blown oxygen lances operate
from subsonic to supersonic velocities and the proportion
of oxygen reacting with the bath, as opposed to providing
post-combustion of carbon monoxide, ranges from 30 to
100% depending on lance height above the bath, nozzle
design and gas velocity (Choulet, 1997).

Argonoxygen decarburisation refractories

Refractory materials are one of the major operating
costs in the AOD process, with the average lining life
being 600 heats and specific refractory consumption
y6 kg t21 of steel (Amavis, 1990). Refractory wear is
not even, but is concentrated around and above the
tuyeres, because fluid velocities are higher in those areas
and around the slag line. Differing grades and thicknesses of refractories are therefore used in different parts
of the vessel. Chromemagnesite refractories were once
widely used, but nowadays .90% of converters are lined
with dolomite or magnesia enriched dolomite refractories (LWB Refractories, 2010). They offer the lowest
overall cost per tonne of steel and, most importantly,
they allow the use of highly basic slags which facilitate
desulphurisation and improve the recovery of chromium

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Stainless steelmaking through computational thermodynamics: Part 3

4 Carbon removal efciency as function of time during

AOD blow, after Hallsten (2007)

increases from y1500 to 1700uC during the first stage

when carbon oxidation dominates, but then only
increases slowly to 1750uC over the next two stages.
3 Chromium, carbon and silicon contents of bath, and
temperature, for 50 t AOD heat, based on data from
Moore and Marshall (1980)

oxides from the slag. The key to good refractory life is

control of both slag chemistry and bath temperature.
The slag should have a CaO/SiO2 (w/w) ratio of .1?4
and should contain some MgO, supplied from adding a
little dolomite as flux. Bath temperature should be kept
below y1750uC to avoid melting the silicate bonding
phase in the refractory and thus weakening the brick
(Klein et al., 1981). However, the temperature must be
high enough to prevent rehydration of the refractory. As
a result, the vessel must be kept hot between heats using
a burner which should fire into the vessel held in the
horizontal position to minimise heat loss (Williams and
Ludlam, 1978).

Argonoxygen decarburisation blowing practice

It is very difficult to compare blowing procedures from
plants around the world due to the differences in raw
materials, product mix, equipment, practice and economic conditions (Choulet, 1997). When starting with a
bath containing 1?01?5 wt-%C, the most common
blowing practice (Klein et al., 1981; Wijk, 1992; Davis,
1994; Hallsten, 2007) is to use:
(i) an oxygen/argon ratio of 3 : 1 until temperature is
y1700uC and the bath has 0?4 wt-%C
(ii) followed by an oxygen/argon ratio of 1 : 1 until
0?10?2 wt-%C
(iii) then an oxygen/argon ratio of 1 : 3 until the
target of 0?020?03 wt-%C.
For extralow carbon steels, a fourth stage using an
oxygen/argon ratio of 1 : 4 or even 1 : 5 can be used, but
too low a ratio is not practical because the extent of
chromium oxidation is reduced too much (Klein et al.,
1981). Paradoxically, some chromium oxidation is
needed to maintain temperature at very low carbon
contents because little heat is then supplied by carbon
oxidation. Marshall and Moore (1980) have tabulated
data on the progress of a typical heat in a 50 t converter
at a British plant, shown graphically in Fig. 3. Most
carbon oxidation takes place in the first stage, as also
does almost all silicon oxidation. The bath temperature

Carbon removal efficiency

The volume of oxygen required to fully decarburise 1 t of
molten steel containing 1?5 wt-%C is 14 Nm3, assuming
that oxygen only reacts with carbon to form CO(g). In
practice, the oxygen consumption in the AOD, normalised to that required for a 1?5 wt-%C steel bath, is
variously quoted as 30 Nm3 t21 (Moore and Marshall,
1980), 2026 Nm3 t21 (Choulet, 1997) and 2228 Nm3 t21
(Wijk, 1992). It is clear that a considerable fraction of the
oxygen supplied is being used to oxidise other elements, i.e.
silicon, manganese and chromium.
The efficiency of oxygen use is described by the carbon
removal efficiency (CRE), expressed as a percentage, and
is defined (Klein et al., 1981; Wijk, 1992; Hallsten, 2007)
as the instantaneous fraction of injected oxygen which
reacts with carbon. The evolution of CRE throughout the
AOD cycle is reproduced in Fig. 4. The CRE is initially
low because most injected oxygen reacts with silicon,
which is the most thermodynamically favoured reaction.
After a few minutes, the CRE rapidly rises towards 100%
as carbon oxidation dominates, but then decreases as
chromium oxidation becomes significant at the lower
carbon contents in the bath. At each oxygen/argon ratio
change, the CRE is shown to undergo a step change
increase to 100%, and then sharply decrease. Davis (1994)
reported that the mean CRE during the first stage of
blowing is 65%, for the second stage, it is 45% and 30%
for the third stage, but this is a gross oversimplification.

Decarburisation mechanism
Reaction (1) is known not to reach equilibrium (Choulet
et al., 1971), with the extent of decarburisation also being
a function of such variables as the depth of submergence
of the tuyeres. Fruehan (1975) was the first to propose a
mechanism for the decarburisation of stainless steel melts.
He envisaged that when the oxygen/argon mix was
injected through the tuyeres, the dominating reaction is
the oxidation of chromium to Cr2O3 and effectively all
oxygen is consumed. The rising argon bubbles contain
dispersed Cr2O3 particles and they oxidise carbon in the
steel bath. At high carbon contents, the rate of carbon
oxidation is controlled by the rate of supply of oxygen,
but at low carbon content, it is controlled by liquid phase

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Stainless steelmaking through computational thermodynamics: Part 3

5 CaOSiO2CrOx phase diagram under moderately reducing conditions (Morita and Sano, 2004)

mass transfer of carbon. Wei and Zhu (2002a) have

critiqued the many variations of this mechanism that
have appeared in the literature and concluded that all of
them had deficiencies and did not reflect the reality of
AOD refining. They developed a model which was shown
to predict the behaviour of an AOD heat very well (Wei
and Zhu, 2002b). Wijk (1992) also presented a simple
model of the AOD process and showed, as expected, that
when the carbon content of the bath is below some critical
value, then the diffusional control of decarburisation
results in the CRE being decreased below that predicted
by equilibrium considerations.

Heat balance
Temperature increases during the three blowing stages,
as can be seen from Figs. 3 and 4, principally as a result
of silicon and chromium oxidation. The initial silicon
content of the steel bath is important because if it is too
low, the bath will not heat quickly enough and
chromium oxidation, favoured at low temperatures, will
be promoted (Klein et al., 1981). Carbon oxidation is
not significant as a source of heat. High temperatures
favour the oxidation of carbon; however, they lead to
more severe slag attack on the refractories, so temperature control during an AOD cycle is critical to process
success. Conducting a heat balance on the AOD is
difficult because the CRE varies through the heat, the
refractories have different starting temperatures and
their thermal conductivity changes with time due to the
effects of slag attack (Klein et al., 1981).

Slags and fluxing

It is commonly stated that chromium is present during
AOD steelmaking as Cr2O3 and that this oxide has a very
low solubility in slags (Dennis and Richardson, 1953;
Wijk, 1992; Hallsten, 2007). This is only true if the slag is
very oxidised, e.g. in equilibrium with air. During AOD
steelmaking, the slag approaches equilibrium with a bath
containing a large fraction of chromium, so conditions
are very reducing. Liquidus phase relations in the CaO
SiO2CrOx system in equilibrium with chromium were
determined by de Villiers and Muan (1992), while Morita
and Sano (2004) presented the phase diagram at
moderately reducing conditions where the oxygen partial
pressure was 6?95610211 atm. Their phase diagram is

26

most appropriate to AOD converting and is given in

Fig. 5. There is a large liquid region and the chromium
content of the slag can be high at typical CaO/SiO2 ratios.
Saturation with CrO1?5 (Cr2O3) only occurs with very
high CaO/SiO2 ratios under such reducing conditions, but
will occur under typical CaO/SiO2 ratios when the oxygen
partial pressure rises towards the end of each stage of
blowing. When MgO (and possibly Al2O3) are present,
the solubility of Cr2O3 decreases and saturation with the
spinel structure MgO.(Cr,Al)2O3 occurs (Arnout et al.,
2008, 2009).
The greatly increased chromium solubility in slag is due
to the presence of CrO. It has been shown (Xiao et al.,
2002) that for a slag in equilibrium with chromium, the
predominant oxidation state of chromium in slag is 2z,
i.e. CrO. A recent comprehensive examination of the
redox equilibria of chromium in calcium silicate melts
(Mirzayousef-Jadid and Schwerdtfeger, 2009) corroborated these findings and showed that Cr2z comprises
y80% of total chromium at an oxygen partial pressure of
10210 atm and a CaO/SiO2 mass ratio of 1?1 at 1600uC,
decreasing as the CaO/SiO2 increased.
Fluxing practice generally involves adding lime (CaO)
together with some dolomite before charging the AOD
(Klein et al., 1981). The target CaO/SiO2 mass ratio
basicity is 1?4 (Klein et al., 1981) to 1?7 (Wijk, 1992;
Hallsten, 2007). The total CaO requirement depends on
the initial silicon content of the steel bath and the target
CaO/SiO2 ratio in the slag and is variously quoted as
being from 3545 kg t21 (Wijk, 1992) to 5060 kg t21
(Choulet, 1997).

Slag reduction
At the completion of oxidation, the slag will contain
dissolved CrO and Cr2O3, as well as a significant
amount of solid Cr2O3. Most of this can be reduced
back to chromium by additions of a reductant such as
ferrosilicon or aluminium (Klein et al., 1981). The
silicon reduction of chromium oxides can be represented
as
1=2SizCrO~Crz1=2SiO
0

2,

DG ~{66:4 kJ at 1700 C
3=4SizCrO

(2)

3
1:5 ~Crz =4SiO2 ,

DG ~{99:9 kJ at 17000 C

(3)

where the thermodynamic data are taken from the HSC

Chemistry for Windows v.5?1 database (Roine, 1998).
Figure 3 shows that the bath temperature drops by
almost 100uC due to the addition of the cold reductant,
flux and argon for stirring. Silica is formed, so lime is
added to keep the slag basicity high, i.e. to keep the
activity of SiO2 low and therefore favour reactions (2)
and (3). Fluorspar (CaF2) is also added at a rate of
approximately 23 kg t21 (Wijk, 1992) and is needed to
increase the solubility of CaO in the reduction slag,
maintain fluidity as the temperature drops and therefore
also increase the mass transfer rate of the reduction
reactions (Pretorius and Nunnington, 2002). Reduction
in the AOD is particularly fast and effective because
argon stirring gives excellent slag/metal contact and
rapid dissolution of the CaO into the slag (Klein et al.,
1981). The silicon content of the steel increases as the
activity of CrO and CrO1?5 in slag decreases. The extent

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of chromium oxide reduction is limited by the silicon

specification of the steel, with most stainless steels
limited to 0?30?5 wt-%Si. The amount of ferrosilicon
(75 wt-%Si) required for reduction depends on the
chromium content of the slag and the final silicon
content of the steel, but is typically 811 kg t21 (Wijk,
1992; Choulet, 1997).

Methodology
HSC simulation
The HSC Chemistry for Windows v.5?1 software
package (Roine, 1998) was utilised in this work. It was
successfully used in two previous publications to model
EAF melting of steel scrap (Kho et al., 2010) and VOD
refining of stainless steel (Swinbourne et al., 2010). All
likely phases in the system; the species which are in or
likely to be created in each phase; the activity coefficients
of all species in each phase; the masses of all input
species, the temperature and the pressure of the system
must be specified. A Gibbs free energy minimisation
routine is used in HSC to output the quantities of all
species in all phases at equilibrium.
HSC can only utilise constant values of activity
coefficient, so slag species were represented in the
monocation form because this leads to activity coefficient values which are approximately constant over a
wide range of concentrations (Yazawa et al., 1983).
The species CrO(l) is not included in the HSC
database, so it needs to be added using the data of Toker
et al. (1991) as described by Kho et al. (2010). The data
for CrO(l) in standard HSC format have the following
parameters: H52334?218 kJ mol21, S562?400 J mol21 K21,
A532?430, B520?958, C520?381 and D522?623.
Early thermodynamic analyses (e.g. Dennis and
Richardson, 1953) did not consider the existence of CrO
in slag. A line representing the oxygen potential of the Cr/
O2(g)/CrO(l) reaction, based on the Toker et al. (1991)
data, could be added to Fig. 1. If the activity of CrO(l) is
assumed to be 0?1 and the activity of chromium in the
alloy 0?2, then the line would be only y20 kJ below that
for Cr/O2(g)/Cr2O3. As a result, the previous conclusions
relating to the effect of CO(g) partial pressure on
the relative oxidation of chromium and carbon remain
valid.

Model basis
The slag was taken to contain CaO, SiO2, CrO, CrO1?5,
FeO and MnO. It was assumed that the slag formed
would lie in the liquid region given in Fig. 5, and that
the saturating solid phase would be Cr2O3. This is
reasonable as saturation with a spinel phase only occurs
when MgO and possibly Al2O3 are present (Arnout
et al., 2008, 2009). There are databases for several forms
of silica in HSC, and in this work, silica was taken to be
cristobalite, represented as SiO2(CRS) in the HSC
database. NiO was not considered because under the
prevailing oxygen partial pressures, nickel oxidation is
insignificant. MgO from dolomite flux or refractory
attack was also neglected. The amounts of CaO used in
the modelling were those which gave a final CaO/SiO2
mass ratio of 1?61?7 at the completion of oxidation and
reduction. No CaF2 addition to slag was included because
its presence would have no affect on the predicted
equilibrium outcomes.

Stainless steelmaking through computational thermodynamics: Part 3

The model blowing practice was defined as follows:

(i) the first stage: an O2/Ar ratio of 3 until 0?4
wt-%C, and a mean temperature of 1615uC
(ii) the second stage: an O2/Ar ratio of 1 until
0?15 wt-%C, and a mean temperature of 1680uC
(iii) the third stage: an O2/Ar ratio of 1 : 3 until
0?02 wt-%C, and a mean temperature of 1705uC.
A separate HSC model was used for each stage, with the
mass of condensed species present at the end of one
stage being the input values for the subsequent stage.
During the reduction stage, the reductant was taken to
be pure silicon. The amount of iron added with the typical
75 wt-%Si ferrosilicon alloy used is not significant compared with the total amount of iron present in the bath. The
average bath temperature was assumed to be 1700uC.

Slag activity coefficients

The activity coefficients of CaO(s) and SiO2(s) were
those calculated by Xiao and Holappa (1997) for the
CaOSiO2CrOx system at 1600uC in equilibrium with
pure chromium. The values obtained were close to those
used in previous work (Kho et al., 2010; Swinbourne
et al., 2010) using a regular solution model (RSM) (BanYa, 1993). The activity coefficients of CrO(l) and
CrO1?5(s) in slag are important parameters in this work.
Morita and Sano (2004) reported that the activity
coefficient of CrO1?5(s) is y10 and that of CrO(l) y50
at high slag basicity and at 1600uC. Such a high value for
CrO(l) is not credible and is likely to be a result of
unwanted oxidation during the very difficult titrations
used to determine Cr2z in solution. Xiao et al. (2002)
used the electromotive force method to measure the
activity coefficients of the chromium oxides at 1600uC
and from their data, the value can be taken as 5 for
CrO(l) and 8 for CrO1?5(s), although there is a
considerable degree of uncertainty because the values
of the activity coefficients depend on basicity and the
chromium content of the slag. These values are very
different from those from the RSM, which gave values
of only 3 for CrO(1) but 15 for CrO1?5(s). Experimental
data are to be preferred, so the values of Xiao et al.
(2002) will be used in this work. The activity coefficients
of the minor species FeO(l) and MnO(s) were calculated
using the RSM and have a minimal impact on the model
predictions. The RSM indicated that all slag species
activity coefficients were not significantly affected by
temperature over the range of 16001700uC, so the same
values will be used in all stages in the model.

Metal activity coefficients

Activity coefficients in the molten iron phase were
estimated in the same way as detailed previously (Kho
et al., 2010). The values of the activity coefficients of all
elements except carbon were not significantly affected by
temperature over the range of 16001700uC. However,
the limiting activity coefficient of carbon varied from
0?35 at 1600uC to 0?25 at 1700uC, so the mean value of
0?3 was taken as satisfactory for this work.

HSC model inputs

The phases, species, activity coefficients and input
masses for the three oxidation stages and the reduction stage are given in Table 1. The initial molten steel
bath was taken to contain 18 wt-%Cr, 10 wt-%Ni, 0?5
wt-%Mn, 0?3 wt-%Si and 1?5 wt-%C. No slag carryover
from the EAF was considered.

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Stainless steelmaking through computational thermodynamics: Part 3

6 Masses of several species as function of mass of

injected oxygen during rst stage, at O2/Ar ratio of 3 : 1
and temperature of 1615uC

The output masses of all condensed species became

the input masses for the subsequent model. Output
masses of gaseous species were not passed to the next
stage. Oxygen and argon step sizes were in the appropriate ratio for each oxidation stage.

Results and discussion

First oxidation stage
The masses of important species as a function of the
amount of oxygen blown are given in Fig. 6. Solid Cr2O3
begins to form just as the carbon content of the bath
reaches 4 kg, i.e. very close to 0?4 wt-%C, which is the
endpoint expected. The amount of oxygen required to
reach this endpoint is y22 kg t21 (16 Nm3 t21). Silicon
is oxidised to very low levels, while significant manganese
oxidation also takes place. The model also predicts that
for most of this stage of blowing, chromium is present in
the slag in almost equal amounts of both CrO and CrO1?5.

7 Carbon removal efciency as function of mass of

injected oxygen during rst stage, at O2/Ar ratio of 3 : 1
and temperature of 1615uC

The CRE, given in Fig. 7, was calculated incrementally for each step of the simulation as the percentage of
injected oxygen which reacted to form CO(g) and
CO2(g). The form of the CRE curve is similar to that
shown in Fig. 4. Most noticeable is the sharp drop in
CRE once Cr2O3 saturation of slag occurs, so blowing
should not continue into this region.
In the first stage, where the rate of supply of oxygen is
the limiting factor (Fruehan, 1975), it would be expected
that the model should predict the amount of oxygen
required to reach the carbon target of 0?4 wt-% quite
well. However, there are very little data in the literature
under equivalent operating conditions which can be used
for comparison. It can be calculated from information
given by Moore and Marshall (1980) that the oxygen requirement in the first stage is 13 Nm3 t21 and
this compares quite well with the predicted value of

Table 1 Species, activity coefcients and input masses (kg) for HSC models used during all stages of AOD cycle
Species
Gas
O2(g)
Ar(g)
CO(g)
CO2(g)
SiO(g)
MnO(g)
Slag
CaO(s)
SiO2(CRS)
CrO(l)
CrO1.5(s)
FeO(l)
MnO(s)
Metal
Fe
Cr
Ni
Mn
Si
C
Pure
CaO
Cr2O3
Si

28

Activity coefficient

First stage

Second stage

Third stage

1
1
1
1
1
1

Step
Step

Step
Step

Step
Step

0.15
0.1
5
8
1
0.1
1
0.9
1
1.2
0.002
3
1
1
1

Reduction

10
6.3
3.2
4.3
0.7
5.3

10
6.2
3.6
4.6
1.0
5.3

25
6.2
3.7
4.6
1.2
5.3

697
180
100
5
3
15

696
174
100
0.9
0.7
3.8

696
174
100
0.9
0.1
1.8

696
170
100
0.9
0.1
0.2

10

5.9
Step

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Stainless steelmaking through computational thermodynamics: Part 3

8 Masses of several species as function of mass of

injected oxygen during second stage, at O2/Ar ratio of
1 : 1 and temperature of 1680uC

10 Masses of several species as function of mass of

injected oxygen during third stage, at O2/Ar ratio of
1 : 3 and temperature of 1705uC

16 Nm3 t21. Stoichiometric calculations show that the

amount of oxygen required to oxidise carbon from 1?5
to 0?4 wt-% is 10?3 Nm3 t21, and noting that the
average CRE for this stage is estimated at 65% (Davis,
1994), the actual oxygen requirement should be
15?8 Nm3 t21. This match is excellent.

supplied from a source other than that being injected.

When the oxygen/argon ratio is dropped from 3 : 1 to
1 : 1, the slag becomes overoxidised with respect to the
new oxygen partial pressure, so metal oxides in the slag
react with carbon in the bath. This can be seen in Fig. 8
as a lower mass of carbon at zero oxygen addition than
the final mass of carbon at the end of the first stage, a
small decrease in the masses of CrO and CrO1?5 up to
1 kg t21 of oxygen and a slight increase in the mass of
manganese in the steel.
Wijk (1992) referred to the overoxidised state of the
slag as a result of changing the O2/Ar ratio and implied
that this results in carbon oxidation by indicating that
some AOD operators blow only argon as a fourth stage
to further lower the carbon content of the bath. Clearly,
this can only take place via reaction with metal oxides in
the slag. Klein et al. (1981) stated that CRE values
.100% are unattainable, but this is incorrect. In
practice, CRE values over 100% are unlikely to be
observed because they require that the slag and metal
bath be perfectly mixed. The CRE drops to y50%
before Cr2O3 forms, so the average CRE will be
somewhat greater than 45% as given by Davis (1994).
Comparison of the predicted oxygen requirement with
the literature is not possible or meaningful for the
second and third oxidation stages. Both stages for the
example from Moore and Marshall (1980) used different
O2/Ar ratios from those in this work. In addition, the
extents of metal oxide reactions with carbon in practice
will be much less than those in this model.

Second oxidation stage

The masses of important species as a function of the
amount of oxygen blow in the second stage are given in
Fig. 8. It can be seen that further carbon removal occurs
without the formation of solid Cr2O3, and with only
small increases in the masses of dissolved chromium
oxides. Solid Cr2O3 begins to form at 3 kg t21 of
oxygen, just as the carbon content of the bath reaches
1?8 kg, i.e. y0?18 wt-%C. This is close to the expected
endpoint of 0?15 wt-%C, which could be reached by
allowing the formation of some Cr2O3. The manganese
content of the steel bath drops a little further, but the
silicon content remains almost constant. It can be seen
from Fig. 3 that, in practice, a little silicon oxidation is
expected in the second stage.
The evolution of the CRE for the second stage as a
function of the mass of oxygen injected is given in Fig. 9.
The CRE is initially over 100%, indicating that oxygen is

Third oxidation stage

9 Carbon removal efciency as function of mass of

injected oxygen during second stage, at O2/Ar ratio of
1 : 1 and temperature of 1680uC

The masses of important species as a function of the

amount of oxygen blow in the third stage are given in
Fig. 10. Again more carbon removal occurs after the
change in O2/Ar ratio before any solid Cr2O3 forms.
However, it can also be seen that the carbon content of
the bath does not reach the target of 0?2 kg (0?02
wt-%C) even after large amounts of solid Cr2O3 have
formed.
HSC Chemistry for Windows functions in a closed
system mode. As oxygen and argon amounts are
incremented, all output species from step n becomes
the inputs to step nz1, so all CO(g) formed in previous
steps is retained during calculation. In practice, it is
likely that most CO(g) formed in the AOD is rapidly

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Swinbourne et al.

Stainless steelmaking through computational thermodynamics: Part 3

11 Mass of carbon as function of mass of oxygen blown

during third stage under closed system conditions
and under simulated open conditions

flushed from the converter, so that the process can be

considered to operate in an open system mode. The
result will be a lower CO(g) partial pressure and
therefore lower carbon contents in the steel bath. HSC
cannot calculate in open mode, but this can be
simulated by dividing the third stage into five substages.
Only the masses of condensed species are passed
manually from one substage file to the next. The results
are shown in Fig. 11 and it can be seen that the target
carbon content of 0?02 wt-%C can be reached and
requires y4 kg t21 of oxygen (3 Nm3 t21). The difference between closed and open modes of calculation is
insignificant at the higher carbon contents in the first
two stages.
The CRE is shown in Fig. 12 and again, for the same
reason as in the second stage, the initial CRE value
exceeds 100%. The CRE rapidly decreases and it can be
seen that the average CRE of 30% suggested by Davis
(1994) is reasonable. Under open system conditions, the
CRE values are minimally affected because they only
result in very small changes in the carbon content of the
steel bath.

Reduction stage
The amounts of species present at 4 kg t21 of oxygen
addition were used as the input data to the reduction

13 Masses of some important species in slag and metal

bath as function of mass of silicon added, at 1700uC

model, as given in Table 1. The amount of CaO was

increased to that sufficient to achieve the target CaO/
SiO2 (wt-%) of 1?61?7 when the silicon content of the
bath reached 0?5 wt-%.
The masses of important slag and metal species as a
function of the mass of silicon added are given in
Fig. 13. No Cr2O3 appears because CaO has been added
to the slag and the model predicts that all Cr2O3 then
dissolves into the enlarged slag mass. The masses of
chromium oxides in the slag initially decrease quickly
but never reach zero. The mass of silicon in the steel
bath rises steadily, but commercial stainless grades limit
the silicon content to a maximum of y0?5 wt-%. This
limit is reached at an addition of 9 kg t21, which is
equivalent to 12 kg t21 of 75 wt-%Si ferrosilicon. This
compares acceptably with typical ferrosilicon consumptions of 811 kg t21 (Wijk, 1992; Choulet, 1997).
It can be estimated from Fig. 13 that the remaining
mass of chromium in the slag is y2 kg t21. The initial
mass of chromium in the bath was 180 kg t21, so the
overall chromium recovery to the steel is 99%. Chromium
recoveries in practice are given as being in the range of
97100% (Klein et al., 1981; Davis, 1994), in agreement
with the model.
Overall, the consumption of CaO predicted by the
model was 25 kg t21 while Wijk (1992) gave typical
consumptions as 3545 kg t21. This difference is not due
to differing assumptions of the initial silicon content of
the steel. This model assumed that no slag was carried
over from the EAF to the AOD, while in practice some
carryover is to be expected and additional CaO may be
needed to flux the SiO2 in this carryover slag. No
information on expected amounts of slag carryover
could be found in the literature. In addition, the CaO/
SiO2 ratio (w/w) may have been higher than that
assumed in this work, so improved desulphurisation of
the melt could be achieved.

Model evaluation

12 Carbon removal efciency as function of mass of oxygen injected during third stage when O2/Ar ratio is
1 : 3 and mean temperature is 1705uC, for both closed
and open conditions

30

A simple thermodynamic model of the AOD practice

cannot be expected to predict all operating parameters
accurately because it is known that kinetic factors also
play a role in operation of the AOD. Additionally, the
values of the activity coefficients of important slag
species are uncertain and had to be assumed to be
constant for all stages due to the limitations of the
software package. Finally, temperature was assumed

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constant during each stage and EAF slag carryover,

MgO addition via dolomite flux or refractory attack and
the addition of fluorspar to the reduction slag were not
considered. A model which predicts the correct trends in
outputs as input variables are altered and leads to
improved understanding of the process is what is required
in the educational context.
The primary aim of the modelling was to illustrate how
diluting the oxygen blown into the AOD converter with
increasing amounts of argon allows very low carbon
contents in the stainless steel bath to be reached without
excessive chromium oxidation. A secondary aim was to
show how oxidised chromium can be recovered from the
slag, and how this is limited by the silicon specification of
the stainless steel. Both aims have been achieved by a
simple and transparent computational thermodynamic
model which should prove of value to those wishing to
better understand pyrometallurgical processes.

Conclusion
The three stages of decarburisation using decreasing
ratios of oxygen/argon and the slag reduction stage in the
AOD stainless steelmaking converter were modelled
using computational thermodynamics software. The
way in which this blowing practice could achieve very
low carbon levels in the molten steel bath without excessive co-oxidation of chromium was illustrated. The
CRE was calculated for each stage and shown to be a
good match with existing plant data. Additions of silicon
in the form of ferrosilicon were also shown to be effective
in reducing chromium oxides from the slag, but the extent
of reduction is limited by the accompanying increase in
the silicon content of the steel. Despite the simplicity and
transparency of the models, they correctly predicted all
trends in output variables as input parameters were
changed and in most cases matched plant data very well.
The models will be a valuable learning tool for those
interested in pyrometallurgical processing.

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