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Understanding stainless steelmaking through computational

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Understanding stainless steelmaking through
computational thermodynamics
Part 1: electric arc furnace melting
T. S. Kho1, D. R. Swinbourne*1, B. Blanpain2, S. Arnout2 and D. Langberg1
Stainless steel alloys are widely used in many important applications but their production presents
difficulties because they contain expensive chromium, which can be extensively oxidised during
decarburisation to the very low carbon levels required. Modern stainless steelmaking largely
avoids this problem by having two distinct stages and is therefore described as duplex practice.
Molten high carbon stainless steel is produced in an electric arc furnace and then the melt is
decarburised in an argon–oxygen converter or a vacuum oxygen decarburising converter. In this
work, computational thermodynamics has been used to examine the major reactions occurring in
the electric arc furnace and to show the effect of various process variables on chromium recovery.
It was shown that significant oxidation of the scrap must occur during melting, and that
subsequent carbon/oxygen injection initially oxidises some chromium, but then mostly oxidises
the added carbon. Chromium was predicted to exist in the slag as CrO and CrO1?5 in almost equal
proportions. Increasing the temperature should improve chromium recovery but results in less
benefit than expected due to the decreasing activity coefficients of CrO and CrO1?5 and the
increasing oxygen partial pressure. Ferrosilicon additions reduce chromium oxides from the slag,
but much of the silicon simply dissolves into the steel. Computational thermodynamics is seen to
be a very effective educational tool for gaining an understanding of smelting processes.
Keywords: Electric arc furnace, Stainless steel, Thermodynamics, Computational model

Introduction necessary to ensure that grain boundary corrosion will

Introduction to stainless steels
Stainless steels are iron based alloys containing a
minimum of 10 wt-%Cr and varying amounts of other
alloying elements. Table 1 shows the composition of
several widely used grades of stainless steels. The
minimum chromium content is determined by the need
for a passive film of chromium oxide to form on the
surface, which prevents aqueous corrosion. Corrosion
and staining resistance, low maintenance and familiar
lustre make stainless steels ideal materials for a host of
commercial applications including cookware, cutlery,
hardware, surgical instruments, industrial equipment
and structural applications in the automotive and
aerospace industries. Importantly, stainless steel is
recyclable, any stainless steel object typically containing
60% of recycled material – 25% from end-of-life
consumer products and 35% being scrap from manu-
facturing processes.1 Very low carbon contents are
1
School of Civil, Environmental and Chemical Engineering, RMIT
University, 124 Latrobe Street, Melbourne 3000, Australia
2
Departement Metaalkunde en Toegepaste Materiaalkunde, Katholieke
Universiteit Leuven, Kasteelpark Arenberg 44, B 3001 Leuven, Belgium
*Corresponding author, email drs@rmit.edu.au
not take place.3
Carbon is removed from steels by oxidation, carbon
being much more readily oxidised than iron, as can be
seen on the Ellingham diagram given as Fig. 1. The
vertical axis will be DGu, the standard Gibbs free
energy change, for all lines except those for a reduced
carbon activity, for which it will be the general Gibbs
free energy change DG. Chromium is clearly much
more readily oxidised than iron. At y1200uC the
oxidation of carbon and chromium at unit activity are
equally likely, but as the temperature is increased
carbon becomes increasingly favoured. As carbon is
oxidised to very low levels its activity drops rapidly and
the C/O2/CO line on the Ellingham diagram rotates
upwards, which therefore makes chromium oxidation
increasingly favourable. The main issue with producing
stainless steel is the restriction imposed by the carbon–
chromium equilibrium,4 i.e. the need to oxidise carbon
without also oxidising much chromium. Failure to
develop a strategy to achieve this would lead to
excessive loss of chromium and necessitate the addi-
tion of expensive low carbon ferrochromium to achi-
eve the required grade of stainless steel, without
simultaneously increasing the carbon content beyond
specifications.

ß 2010 Institute of Materials, Minerals and Mining and The AusIMM

Published by Maney on behalf of the Institute and The AusIMM
Received 18 March 2009; accepted 16 August 2009 Mineral Processing and Extractive
DOI 10.1179/174328509X431454 Metallurgy (Trans. Inst. Min Metall. C) 2010 VOL 119 NO 1 1
Kho et al. Understanding stainless steelmaking through computational thermodynamics: Part 1

2 Electric arc furnace8

1 Ellingham diagram for relevant iron, chromium and car-
bon oxidation reactions: range of steelmaking tempera-
tures is shaded
Stainless steelmaking technology
In the early days of stainless steel production carbon
steel scrap, iron ore and lime (CaO) were charged into
an electric arc furnace (EAF). When the charge was
molten, ferrosilicon, lime and fluorspar (CaF2) were
added and the temperature of the bath was increased so
that a large amount of low carbon ferrochromium could
be added.5 With the advent of tonnage oxygen, oxygen
injection into the molten steel using a lance greatly
improved the rate of decarburisation. However, the
more oxidising conditions had the expected adverse
effect of extensive oxidation of chromium to the slag. A
reduction period using ferrosilicon to reduce the
oxidised chromium from the slag became necessary
before low carbon ferrochromium could be added.
Modern stainless steelmaking practice does not
attempt to make stainless steel in an EAF alone. The
EAF is used to provide a molten steel charge for
converters, without any significant decarburisation of
the melt and with minimum chromium oxidation to the
slag. The melt is then decarburised in a variety of
converters, with argon oxygen decarburisation (AOD)
and vacuum oxygen decarburisation (VOD) being the
most widely used. As a result, these practices are
classified as ‘duplex’ in that there are two stages in the
production of stainless steel. Sometimes further refining
takes place under vacuum to produce stainless steels
which have very low carbon and nitrogen requirements
and this is known as ‘triplex’ practice.5
In this work, only the chemical reactions taking place
during EAF melting will be discussed and modelled
using computational thermodynamics. A mathematical
model designed to predict the compositions of slag and
steel as a function of time has been described by Arnout
Table 1 Composition ranges for typical grades
stainless steels,2 wt-%
Grade Classification C Mn Cr Ni
304 Austenitic 0.05 1.5 18.5 9 …
310 Austenitic 0.08 1.5 25 20
316 Austenitic 0.05 1 17 11
410 Martensitic 0.1 0.5 12 … …
430 Ferritic 0.03 0.4 16.5 … …
et al.6 and was intended to understand the chemistry of
the process as well as to be used as an aid to control
stainless steelmaking operations. This work has an
educational focus and will utilise the HSC Chemistry
for Windows software package as a tool for gaining an
understanding of the chemical changes taking place
within the EAF. A subsequent paper will take the same
approach to examine decarburisation of molten stainless
steel in AOD and VOD converters.
The duty of the EAF is to efficiently and economically
deliver molten metal of the required composition and
temperature to a converter. The EAF is the most widely
employed melter due to its ability to process a wide
variety of raw materials.5 An EAF, as shown schema-
tically in Fig. 2, consists of a refractory lined hearth,
vertical cylindrical sidewalls, and a removable roof.7
Graphite electrodes pass through holes in the roof and
are clamped to arms which move vertically on masts
mounted to the furnace assembly. This allows the
electrodes and roof to be raised and swung to one side
to allow furnace charging. Conventional furnaces have a
horizontal tapping spout where the entire furnace can be
tilted for tapping, while some prefer eccentric bottom
tapping furnace because it allows slag free tapping and
decreased steel temperature losses during tapping.8
Power is supplied from a three-phase, multivoltage tap
transformer to three carbon electrodes, though some
furnaces use dc power and have only one or two
electrodes.
Many modern EAFs are equipped with oxy fuel
burners and lances for injecting oxygen, lime and carbon
to increase the energy input into the furnace and reduce
melting cycle times. In such furnaces y60% of the
energy input is electrical with the remainder being
chemical energy from oxy fuel combustion, oxidation of
silicon and carbon and other chemical reactions.7
Carbon and oxygen injection also generates a large
volume of carbon monoxide gas and so can cause the
slag to foam around the electrodes, as will be discussed
later.
of A typical heat commences with the charging of a total
of y10 t carbon steel scrap, 90 t stainless steel scrap and
Mo 10 t high carbon ferrochromium (50 Cr, 7 C, 4 Si,
balance Fe, wt-%) through the open roof of the furnace.
The roof is then swung into place, the electrodes are
… lowered and current flow is initiated so that the
2 electrodes bore through the scrap to form a pool of
liquid metal. About 5 t fluxes containing mostly lime
(CaO) and some magnesia (MgO) are added soon after.

2 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2010 VOL 119 NO 1
 Kho et al.
When the scrap is fully melted, carbon in the form of
coke (y300 kg) is added to the steel bath together with
y250 Nm3 of oxygen which is injected through a lance
over a period of y10 min.
After the oxygen blow, y900 kg of 75 wt-%Si
ferrosilicon is added to reduce chromium oxides from
the slag according to the reaction
3Siz4CrO1:5 ~4Crz3SiO2
DG 0 at 16000 C~{422 kJ
DH 0 at 16000 C~{588 kJ
In order to improve slag/metal contact, argon or
nitrogen is often injected through a bottom plug. Guo
et al.9 reported that this bottom stirring is largely
ineffective in promoting the reduction of chromium
oxides by silicon. Most reduction was found to take
place in a spout-tapped EAF during the tapping of slag
and molten steel into the ladle. Strong mixing of slag
and metal is achieved in a spout-tapped furnace because
slag is tapped first, then steel pours onto the slag.
Reduction was minimal in a bottom tapped furnace
where the steel is tapped first, followed by the slag, and
mixing is therefore much less vigorous.
The silica content of the slag increases during
reduction and the slag becomes more viscous, so before
tapping y100 kg fluorspar (CaF2) and 150 kg borax
(Na2O.2B2O3) is usually added to reduce the viscosity.
The tap-to-tap time is y1 h and produces y100 t
molten metal and 15 t slag.
The carbon–chromium equilibrium
An understanding of the competitive oxidation equili-
brium of carbon and chromium is the key to stainless
steelmaking. While carbon simply oxidises to carbon
monoxide gas, there is some dispute regarding the form of
chromium oxide in the slag. Hilty10 suggested that the
stable oxide of chromium in the decarburisation reaction
above 1711uC is CrO. Dennis and Richardson11 stated
that it had been established that Cr2O3 is the stable oxide
of chromium below 1400uC but did not discuss which
oxide was stable at higher temperatures. Similarly,
Fruehan12 assumed that chromium oxidizes to Cr2O3
and did not mention CrO as a possible species, although
in a subsequent publication Kerr and Fruehan13 stated
that CrO was the predominant form of chromium oxide
in slag. Voj et al.14 took both oxidation states of
chromium into consideration by using the oxidation
reactions for both CrO and Cr2O3 in their analysis, while
Sun et al.15 considered the carbon–chromium equilibria
assuming that Cr3O4 was the stable oxide, i.e. that there
were equal numbers of moles of CrO and Cr2O3 formed.
Assuming for simplicity that the carbon–chromium
equilibrium can be expressed satisfactorily as follows, as
was adopted by several authors8,11
2Crz3CO(g)~2CrO1:5 z3C
DG 0 at 16000 C~173 kJ
DH 0 at 16000 C~{77 kJ
The equilibrium expression can be expressed as
(aCrO1:5 )2 (ac )3
K~
(aCr )2 (pCO )3
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
Understanding stainless steelmaking through computational thermodynamics: Part 1
(1)
3 Equilibrium carbon and chromium contents as function
of temperature
Dennis and Richardson11 argued that CrO1?5 had such a
very low solubility in slag that the slag would be
saturated with CrO1?5, so its activity could be taken as
unity. The partial pressure of CO could also be taken to
be 1 atm. Taking the mole fractions of carbon and
chromium in steel to be proportional to their weight per
cent concentrations
K’~(cC wt-%C)3 =(cCr wt-%Cr)2 (4)
The chromium contents of stainless steel in equilibrium
with various carbon contents, as a function of tempera-
ture, can then be graphed as in Fig. 3.
Dennis and Richardson11 did not state the values they
used for the activity coefficients, but their results are
consistent with the assumptions that chromium forms an
ideal solution and that the activity coefficient of carbon
is y0?5. The isotherms in Fig. 3 show that as the carbon
content decreases, so does the chromium content. At a
temperature of 1600uC, an alloy containing 18 wt-%
chromium has an equilibrium carbon content of
y0?42 wt-%. Decarburising below this carbon content
leads to a loss of chromium to the slag. If the melt were
decarburised to ,0?08 wt-% carbon as required by most
stainless steel grades, the chromium content would be
reduced to ,5 wt-% which is well below that required. It
can also be seen that increasing the temperature allows
lower carbon contents at any given chromium content.
For the 18 wt-% chromium alloy, the equilibrium
carbon content can be decreased to 0?1 wt-% if the
temperature is raised to 1800uC. While higher tempera-
tures permit greater extents of decarburisation there are
a number disadvantages, including higher energy costs
and higher refractory consumption.
In practice EAF slags are not necessarily saturated
(2) with chromium oxides so the values of the activity
coefficients of CrO and CrO1?5 in slag are significant,
and depend on the composition of the slag. Maximising
the values of these activity coefficients is desired because
(3) this minimises the concentration of chromium oxides in
2010 VOL 119 NO 1 3
Kho et al. Understanding stainless steelmaking through computational thermodynamics: Part 1
4 Liquid region at 1600uC in CaO–SiO2–MgO–5 wt-%Al2O3
system16
slag and therefore minimises chromium losses. Stainless
steelmaking slags contain mostly CaO, SiO2, MgO and
Al2O3 and the relevant phase diagram at 5 wt-% Al2O3
is given as Fig. 4.16
Silica (SiO2) is formed by the oxidation of silicon in
the scrap steel charge, lime (CaO) is needed to flux the
silica and produce a fluid and basic slag and magnesia
(MgO) is required to reduce the rate of attack of the slag
on the chrome-magnesite furnace refractories.17 The
most important chemical property of the slag is its
basicity. Pretorius and Muan18 and Pei and Wijk19
found that the activity coefficients of CrO and CrO1?5 in
the slag increase with increasing basicity, although both
defined basicity a little differently. Pretorius and Muan
defined basicity as wt-%CaO/wt-%SiO2 while Pei and
Wijk defined it as (NCaO zNMgO )=NSiO2 where Ni is the
mole fraction of ‘i’ in the slag. Gőrnerup and
Jacobsson20 also confirmed the relationship between
slag basicity and chromium recovery to the steel using
industrial data. Figure 4 shows that at 1600uC the
maximum basicity of the slag is obtained at the point
where the slag is double saturated with Ca2SiO4 and
MgO. In practice, the slag may also be saturated with
MgO.Cr2O3. Guo et al.9 examined quenched slag
samples and mainly observed idiomorphic crystals of
MgO.Cr2O3, although they stated that crystals of
(Ca,Mg)2SiO4 were sometimes also seen. The presence
of MgO.(Cr,Al)2O3 spinel in slag was confirmed by Guo
et al.9 early during a heat but in some heats it had
disappeared in the final slag.
Guo et al.9 reported on the evolution of the chromium
oxide content of the EAF slag throughout the melting
process. They showed that at ‘flat bath’, where the steel
has charge has fully melted but before oxygen injection
commences, the slag already contains a large concentra-
tion of CrOx. This clearly shows that a significant
amount of oxidation of the charge takes place during
melting as a result of air ingress into the furnace and
possibly the presence of some rust on steel scrap. During
oxygen injection the CrOx content of the slag rises
4 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
further, but then decreases until at the end of injection it
is only a little lower than it was prior to injection.
Following ferrosilicon addition the CrOx content of the
slag drops rapidly, as described earlier.
Making slags which foam and surround the electrodes
in the EAF is standard practice in carbon steelmaking.
Foam shields the refractories from the arcs so longer,
more powerful arcs can be used and productivity is
therefore increased. Slag foaming in stainless steel
practice is utilised, but is difficult to achieve, partly
because of the presence of solid particles in the slag but
especially because the rate of generation of carbon
monoxide from carbon reduction of chromium oxides in
the slag is much too low to sustain a foam.13 However,
Gőrnerup and Jacobsson20 claim that this is not true in
practice and that significant carbon reduction of
chromium oxides does take place.
The carbon monoxide partial pressure pCO is also a
very significant variable affecting the carbon–chromium
equilibrium, being a cubic term in equation (3). The
lower pCO the greater the equilibrium chromium content
of the steel at any given carbon content. However, in the
EAF pCO cannot be manipulated because the furnace is
open to the atmosphere. Reducing the carbon monoxide
partial pressure is technically possible in converters and
this is the basis of modern stainless steel production. The
pCO can be reduced by either dilution of the input
oxygen with argon as in the AOD converter, or by
reducing the total pressure in the system as in the VOD
converter.
In summary, the processing conditions favourable for
minimising chromium losses during decarburisation are:
(i) operating at as high a temperature as possible
(ii) choosing a slag with the maximum possible
basicity
(iii) minimising the slag volume
(iv) reducing the input partial pressure of oxygen to
reduce pCO
(v) lowering the oxygen partial pressure in the slag
and steel with ferrosilicon additions.
Higher temperatures involve more severe attack on
furnace refractories, while operating with a reduced
oxygen partial pressure increases the time required to
decarburise the steel to the necessary low carbon
contents. If replacement of oxidised chromium is
required, expensive low carbon ferrochrome must be
employed. The evolution of stainless steelmaking
technology has been guided by the need to overcome
or minimise these process constraints.
HSC simulation of the EAF
The ‘equilibrium module’ in the HSC Chemistry for
Windows v.5?1 software package21 is a convenient way
to determine the equilibrium state of a multicomponent
multiphase system. It has been widely used to examine a
variety of complex metallurgical processes.22–25 The
software requires as inputs the specification of 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, and
the temperature and pressure of the system. The
software uses a Gibbs free energy minimisation routine
to output the quantities of all species in all phases at
equilibrium. It cannot take into account rates of
reactions or heat and mass transfer effects, but does
2010 VOL 119 NO 1
 Kho et al. Understanding stainless steelmaking through computational thermodynamics: Part 1

provide valuable information on the effects of process infinite dilution can be calculated from the Gibbs free
variables on the amounts and compositions of molten energy conversion from the pure substance to the wt-%
phases as a function of temperature or the amount of standard states by the following equation
one or more of the inputs.  : 
One problem associated with modelling stainless 0 5585c0i
DGr?wt ~RT ln (8)
steelmaking is that while the software thermodynamic Mi
database is very large, it does not contain data for the where Mi is the atomic weight of species i in g mol21.
species CrO(l). However it is possible to add the required The Gibbs free energies for converting from the pure
data from information in the literature. Toker et al.26 substance to the wt-% standard states were taken from
gave the Gibbs standard free energy change for the the literature.32 All activity coefficients used for species
formation of CrO(l) as follows in the slag and molten steel are given in Table 2. The
3 activity coefficients are given to only two significant
Cr(s)z O2 (g)~CrO(l) figures because they were calculated for representative
2
0 compositions of both phases, so greater precision cannot
DG ~{334218z63:18T J at 1938 to 2023K (5) be justified. Slag was assumed to be 50 CaO–25 SiO2–
Data in the form given in equation (5) is easily entered by 7 CrOx–7 AlO1?5–5 MgO–5 MnO–1 FeO. Steel was assumed
selecting ‘Database’ then ‘Convert data to HSC format’ and to be Fe–18 Cr–8 Ni–1 Mn–0?8 C–0?3 Si (wt-%). It can
following the prompts. The data entry for CrO(l) in the be seen that most of the activity coefficients are not very
standard HSC format has the following parameters: H5 sensitive to temperature, with the notable exceptions
2334?218 kJ mol21, S562?400 J mol21 K21, A532?430, being CrO(l) and CrO1?5(s) in the slag and silicon in the
B520?958, C520?381, D522?623. molten steel.
The most difficult issue in modelling is the selection of During the EAF cycle there are two periods during
appropriate values for the activity coefficients of all which chemical changes take place in the melt. The first
species in all phases. Activity coefficients are a function period is when oxygen is blown into the molten steel,
of the concentration of the species in a solution phase, and the second is when ferrosilicon is added to return
but are acceptably close to constant if the species are chromium to the molten steel. These two periods were
expressed in the monocation form.27 The gas phase can modelled separately.
be considered to be an ideal solution at high tempera-
tures so the activity coefficients of all gas species are Oxygen blowing
unity. The activity coefficients of species in the slag The masses of input species were calculated on a per
phase were estimated using the regular solution model,28 tonne of scrap charged basis from the mass balance data
in which the activity coefficients are given by the for a typical heat from ArcelorMittal Stainless Genk in
following equation Belgium. Elements present in small amounts, such as
X molybdenum, were omitted. Fluorspar and borax fluxes
RT ln ci ~ aij Xj2 were also inconsequential to the modelling and so were
XX
 omitted. The phases and species considered, together
z aij zaik {ajk Xj Xk zDGconv (6) with their input masses and activity coefficients, are
where ci is the activity coefficient of species i, aij is the listed in Table 3. The temperature was taken to be
interaction coefficient between species i and j, Xi is the 1600uC throughout this period. Carbon and oxygen
cation fraction of species i and DGconv is the Gibbs free were considered to be injected simultaneously, with the
energy for conversion from the hypothetical regular oxygen being raised incrementally by 0?035 Nm3 steps
solution standard state to the pure solid or pure liquid and the carbon by 0?05 kg, for 80 steps. Oxidation of
standard states. The interaction energies and conversion scrap by air ingress during melting was simulated by
Gibbs free energies were taken from the literature.28,29 initially adding 3 kg/tonne (2?1 Nm3) of oxygen, this
Interaction energies for CrO–MgO and CrO1?5–MgO small amount being found to satisfactorily reproduce the
were estimated by multiple regression of equation (6) CrOx evolution in the slag observed by Guo et al.9
with the data of Pei and Wijk.19 Activity coefficients during oxygen injection.
were not calculated for NiO because it is expected that
those of FeO could be used for NiO, nor for AlO1?5 Table 2 Calculated activity coefficients for species in
because in the modelling it was not considered to slag and molten steel
partition to any other phase.
Temperature,
Activity coefficients in the molten iron phase were
uC 1550 1600 1650 1700 1750 1800
estimated using the dilute solution model described by
Sigworth and Elliott,30 using the tabulation of Lupis31 CrO (l) 12 10 8.6 7.3 6.3 5.5
for the interaction coefficients. The activity coefficients CrO1?5 (s) 27 22 18 15 12 10
are given by the following equation FeO (l) 1.8 1.8 1.8 1.8 1.8 1.9
X j MnO 0.21 0.24 0.27 0.31 0.34 0.38
ln ci ~ ln c0i z eX (7) CaO (s) 0.048 0.048 0.048 0.049 0.049 0.049
j i j MgO (s) 0.074 0.075 0.076 0.078 0.079 0.080
SiO2 (s) 0.14 0.14 0.15 0.15 0.15 0.15
where ci is the Raoultian activity coefficient, c0i is the Cr (l) 0.83 0.83 0.83 0.83 0.83 0.83
Raoultian activity coefficient at infinite dilution, eji is the Ni (l) 0.72 0.74 0.77 0.79 0.82 0.85
binary first order interaction coefficient between species i Mn (l) 1.19 1.18 1.17 1.17 1.16 1.15
and j, and Xj is the mole fraction of species j. The Si (l) 0.0017 0.0021 0.0026 0.0032 0.0039 0.0048
C (g) 0.37 0.36 0.35 0.33 0.32 0.31
temperature variation of the activity coefficient at

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2010 VOL 119 NO 1 5
Kho et al. Understanding stainless steelmaking through computational thermodynamics: Part 1

6 Masses of chromium oxides in slag as function of tem-

5 Equilibrium amount of carbon, manganese and silicon perature for 3 kg of injected oxygen
in steel, chromium oxides in slag and CO in gas during
simultaneous oxygen and carbon injection, at 1600uC
considered, i.e. CrO1?5, MgCr2O4 and Ca2SiO4, were
and with 3 kg/tonne of ingress oxygen
predicted by the HSC model to form over the range of
oxygen addition examined. This is contrary to the
The evolution of the masses of chromium oxides in findings of Arnout et al.6 who predicted the formation of
slag, carbon, manganese and silicon in the steel melt and significant amounts of calcium aluminium silicates and
carbon monoxide in the gas are given in Fig. 5. MgCr2O4.
Initially manganese, silicon and chromium in the steel The HSC module ‘heat and material balances’ was
melt are being oxidised and injected carbon simply used to determine the temperature rise caused by the
dissolves in the steel. Both chromium oxide species are exothermic oxidation reactions occurring during the
formed in approximately equal amounts, although CrO carbon/oxygen injection period. The temperature of the
is predominant. This supports the simplification of Sun slag and steel prior to injection was assumed to be
et al.15 that the carbon–chromium equilibria can be 1600uC while the carbon and oxygen being injected were
considered to produce Cr3O4, i.e. CrO.Cr2O3. No assumed to be at 25uC. The adiabatic temperature rise
carbon is oxidised until about 0?75 kg/tonne of injected was calculated to be 38uC, a significant increase arising
oxygen (3?75 kg of total oxygen). Once carbon oxidation from chemical reactions rather than from more expen-
commences only very minor reduction of chromium sive electrical energy.
oxides from the slag takes place. Typically, 2?5 to 3 kg/ Increasing the furnace temperature is expected to
tonne of oxygen are injected in industrial practice so greatly reduce the loss of chromium to the slag, as
significant formation of CO (g) is to be expected. These indicated by Fig. 3, so this was modelled by constructing
observations support some of the findings from the an HSC input file in which the temperature varied from
modelling performed by Arnout et al.6 i.e. that carbon 1550 to 1800uC and the injected oxygen input was held
injection raises the carbon content of the steel, leads to at 3 kg/tonne. One difficulty with this modelling was
the formation of CO (g) and reduces some chromium that the activity coefficients of the chromium oxides are
from the slag. None of the potentially saturating species strong functions of temperature, as seen in Table 2. In
one case the arithmetic mean values of the activity
coefficients over the temperature range were used, i.e.
Table 3 Input data for the HSC file used to simulate 8?8 for CrO (l) and 19 for CrO1?5 (s). In the second, the
oxygen blowing at 1600uC activity coefficients were given their true values from
Table 2, this requiring six separate input files to be
Species Amount, kg Species Amount, kg
executed. The results are seen in Fig. 6.
Gas Metal It can be seen that the effect of temperature on the
O2 (g) 2.1 Nm3 Fe 718 loss of chromium to the slag is actually quite weak,
CO (g) Cr 190 especially when the activity coefficients of CrO(l) and
CO2 (g) Ni 72 CrO1?5 are allowed to vary with temperature. The
Mn (g) Mn 12
MnO (g) C 8
simplified case using fixed values of the activity
Si coefficient falsely exaggerates the effect of temperature
on chromium loss. The other reason why the chromium
Slag Pure loss does not decrease as quickly as expected is that the
CaO 30 CrO1?5 curves in Fig. 3 were calculated on the assumption that
SiO2 20 MgCr2O4
the carbon monoxide partial pressure remained fixed at
MgO 15 Ca2SiO4
AlO1?5 5 1 atm. HSC can calculate the oxygen partial pressure in
CrO (l) the system and the values were found to be
CrO1?5 1?79610212 atm at 1550uC and 4?08610211 atm at
FeO 1800uC, i.e. the oxidising potential increased by over an
MnO order of magnitude, leading to further stabilisation of
NiO
the chromium oxides.

6 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2010 VOL 119 NO 1
 Kho et al.
7 Masses of chromium oxides in slag, and manganese
and silicon in steel, as function of mass of silicon
reductant added, at 1638uC
Ferrosilicon reduction
The effect of adding ferrosilicon to the EAF was
modelled by creating another HSC input file, where
the masses of inputs were those applicable to an oxygen
addition of 2?5 kg and where the amount of ferrosilicon
added was varied. Steelmakers typically use 75 wt-%Si
ferrosilicon so it was inappropriate to use the species
FeSi from the HSC database in the modelling. Pure
silicon was used as the input species because the iron
content of ferrosilicon plays no part in the reduction
reactions. In practice approximately 9–10 kg of ferrosi-
licon are used per tonne of steel, which contains 6?75 to
7?5 kg of silicon, so the silicon input was varied from
zero to 10 kg. The temperature was assumed to be
1638uC, the temperature of the steel after it has been
heated by carbon/oxygen injection as discussed above.
Silicon (as ferrosilicon) can be seen to effectively
reduce chromium oxides from the slag, the mass of CrOx
in the slag after ferrosilicon addition being only 30% of
that before the addition when 7 kg/tonne of silicon is
used. However, much of the added silicon is not used for
reducing chromium oxides. Some is used to reduce other
metal oxides in the slag, e.g. MnO, but much of it simply
dissolves into the steel. In this example, when 7 kg/tonne
of silicon is used the residual concentration of silicon in
the steel is 0?5 wt-% and y64% of the added silicon has
dissolved into the steel. This is unfortunate because it
causes problems in the subsequent converter refining
stage. More oxygen in the refining process must be
consumed in oxidising excess silicon and the additional
slag formed may impede efficient oxygen transfer to the
steel. Most importantly, silicon oxidises very exother-
mally so the steel in the converter becomes overheated
and this damages the refractories.
The results in Fig. 7 explain various comments in the
literature regarding the role of silicon in steel in
‘protecting’ chromium from oxidation,20 implying that
silicon is sacrificially oxidised in place of chromium.
Equation (1) for the silicon reduction of chromium
oxide shows that low levels of dissolved chromium in
slag must be accompanied by high silicon levels in steel,
as seen in Fig. 7. It has also been found33 that at very
high levels of residual silicon in steel the chromium
recovery to the steel improves very little, as can be seen
in Fig. 7 from the rapidly decreasing extent of
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
Understanding stainless steelmaking through computational thermodynamics: Part 1
chromium reduction from the slag at high silicon addi-
tions. Gőrnerup and Jacobsson20 state that there is no
significant benefit in having .0?4 wt-%Si in steel, which
in this example corresponds to an addition of 6 kg/tonne
of silicon, while Guo et al.9 recommend a maximum of
0?3 wt-%Si in steel. Equation (1) also shows that
chromium losses to slag will be reduced by reducing
the activity of silica in slag and Guo et al.9 comment that
this is another reason why the basicity of the slag must
be maximised during stainless steel melting.
The silicon reduction of chromium oxides is exother-
mic, as shown in equation (1), but a heat balance
revealed that the temperature of the steel was unchanged
after the reduction process. The heat liberated by the
chemical reaction is almost exactly balanced by that
required to heat the ferrosilicon addition from 25uC to
the steel melt temperature.
Conclusions
Computational thermodynamics modelling of reactions
taking place during the melting of steel scrap in an EAF
to produce a melt suitable for further refining into
stainless steel provides valuable insights into the effect of
operational variables on the efficiency of the process. It
has been shown that significant oxidation of the steel
scrap occurs during scrap melting, and that subsequent
carbon/oxygen injection in the EAF initially oxidises
some chromium to the slag, but then mostly forms
carbon monoxide gas. Carbon/oxygen injection also
results in a significant temperature increase of the steel
bath. Chromium exists in the slag in almost equal
proportions of CrO and CrO1?5, with CrO predominat-
ing. Increasing the temperature of the steel results in less
chromium loss to slag, but the effect is not as
pronounced as expected due to the decreasing activity
coefficients of CrO and CrO1?5 and the increasing
oxygen partial pressure in the furnace. Ferrosilicon
additions reduce chromium oxides from the slag and so
enhance the recovery of chromium to the steel melt, but
much of the silicon simply dissolves into the steel and
this presents problems in the subsequent converter
refining stage.
Acknowledgement
The authors wish to thank the staff of ArcelorMittal
Stainless Genk, Belgium, for providing data and for
helpful discussion of their steelmaking practices.
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