CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 35 (2011) 627–635

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CALPHAD: Computer Coupling of Phase Diagrams and

Thermochemistry
journal homepage: www.elsevier.com/locate/calphad

Steelmaking technology for a sustainable society

Tooru Matsumiya ∗
Nippon Steel Corporation, 20-1 Shintomi, Futtsu 293-8511, Japan

article info abstract

Article history: For the reduction of CO2 emission, two major developments are being conducted in COURSE50 (‘‘CO2
Available online 25 March 2011 Ultimate Reduction in the Steelmaking Process by Innovative Technologies for Cool Earth 50’’). The one
is separation of CO2 gas from BFG (Blast Furnace Gas) and recharge of the rest of BFG including H2
Keywords:
and CO into blast furnace. Hydrogen iron ore reduction technology is also going to be developed. The
CO2 emission reduction
other one is amplification of H2 gas from CH4 , for example, in COG (Coke Oven Gas). The produced
Eco-products
City waste recycling hydrogen gas will be supplied to the society or the reformed COG will be charged to blast furnace. In
Less waste emission addition to these drastic challenging technology developments, a variety of measures for CO2 reduction
is under taken. In the frame of Asia–Pacific Partnership on Clean Development and Climate, the best
available technology for energy savings are discussed to be transferred within seven member nations,
which has the effect of 1.27 million ton reduction of CO2 emission a year. By supplying energy saving
steel products to society such as high strength steels for automobiles and ships, which realizes the
fuel consumption reduction, high performance electrical steels for motors and transformers, which
realize electricity loss reduction, and by recycling waste city plastics and tires in steel processes for
hydrogen gas generation, chemical raw material conversion and iron ore reduction, etc., it is expected that
equivalent 10% reduction of CO2 gas emission in steel production is counted. In steelmaking process the
reduction of refining slags contributes materials use efficiency and less emission of unuseful byproducts.
The control and utilization of nonmetallic inclusions, such as deoxidation products, are one of the key
technology for obtaining product performance, which is required in the above-mentioned steel products.
In order to optimize steelmaking process for these purposes, computational thermodynamics is applied.
Optimization of demanganization, and control of chemical composition of nonmetallic inclusions by the
use of computational thermodynamics are mentioned.
© 2011 Elsevier Ltd. All rights reserved.

1. Introduction 2. CO2 breakthrough program

For the realization of sustainable society, a variety of ap- For the reduction of CO2 emission, two major developments are
proaches is considered in steelmaking sector. At the beginning of being conducted in COURSE50 (Fig. 1), which is the program in
iron and steel production sector of Cool Earth 50, the breakthrough
this paper CO2 Breakthrough Program will be introduced. Then, in-
program for CO2 emission reduction in Japan [1]. The one is
cremental reduction programs of CO2 emission will be mentioned:
separation of CO2 gas from BFG (Blast Furnace Gas) and recharge of
best available technology transfer, eco-products supply to the so-
the rest of BFG enriched in CO gas into blast furnace. The separation
ciety, city waste recycle in steel plants, steel plant waste utilization
technology is being developed both by physical adsorption and
in the society and process improvement and development for less
chemical adsorption. In the case of chemical adsorption, amine
emission. The second through the fourth items are the collabora-
based solvent absorbs CO2 gas in BFG and CO enriched gas is
tion between steel manufacturers and the society. At the end, two
obtained for recharge to BF. After that CO2 gas is released from
examples of the use of computational thermodynamics for prod-
the solvent at 120–140 °C. Since the reaction is endothermic, waste
uct and process development including the above-mentioned eco-
heat in steel plant is to be utilized, such as sensible heats of BF slag
product and eco-process are discussed.
and LD slag. The separated CO2 gas is to be stored in oil and gas well
and onshore and offshore aquifers. The storage of CO2 gas is under
development in other projects than COURSE50.
∗ Tel.: +81 439 80 2150; fax: +81 439 80 2769. The other one is amplification of H2 gas from CH4 , tar and
E-mail address: matsumiya.tooru@nsc.co.jp. light oil in COG. Hydrogen gas is contained in COG by about 60%.
0364-5916/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.calphad.2011.02.009
628 T. Matsumiya / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 35 (2011) 627–635

the frame of Asia–Pacific Partnership on Clean Development and

Climate, the best available technology for energy savings are dis-
cussed to be transferred within seven member nations, which has
the effect of 1.27 million ton reduction of CO2 emission in a year.
IEA also estimated that 3.4 million ton reduction of annual CO2
emission is possible by transferring best available technologies in
the world (Fig. 2) [2].

3.2. Eco-products supply

By supplying energy saving steel products to society such as

Fig. 1. Outline of COURSE50 development plan [1].
In the first stage of the program the proof test of the following
hydrogen gas supply system was conducted: hydrogen gas was
separated from COG by using some chemical solvent in hydrogen
production station in Kimitsu Works and transported to hydrogen
supply stations in metropolitan area in Tokyo for fuel cell cars,
etc. The proof test was successful. Since Nippon Steel has steel
works with coke oven batteries from north to south of Japan, it
has advantage in supply of hydrogen gas nationwide. In the second
stage, hydrogen gas amplification has been conducted in Yawata
works. CH4 gas is converted to H2 and CO gas by reforming with
steam or partial oxidation. Tar and light oil are first converted to
CH4 gas by cracking with H2 gas and finally to H2 and CO gas by
reforming with steam or partial oxidation, again. For this cracking
and reforming sensible heat in COG is applied. The produced
hydrogen gas will be supplied to the society or the reformed COG
will be charged to blast furnace. Reduction rate of iron ore with
hydrogen gas is five times faster than reduction rate with CO
gas but it is endothermic reaction. Hydrogen iron ore reduction
technology is also going to be developed with these aspects. ULCOS
program is under taken in Europe as an equivalent program to
COURSE50. They collaborate each other and form IISI (International
Iron and Steel Institute)—CO2 breakthrough program.
3. Incremental reduction programs of CO2 emission
high strength steels for automobiles and ships, which reduces the
fuel consumption, high performance electrical steels for motors
and transformers, which reduce electricity losses, and high perfor-
mance boiler tubes, which increases efficiency of thermal engine
by increasing its operation temperature, steel sector farther con-
tributes to the reduction of CO2 emission. High corrosion resistant
steels and high fatigue resistant steels elongate the lifetime of steel
constructions. High strength steel sheets for automobile plates for
ships and high strength wires for bridges reduce the amount of
steel use for obtaining the unit performance. They contribute to
efficient usage of limited materials resource. Lead free steels, chro-
mate free steel products and polyvinyl chloride free steel products
satisfy environmental regulation laws and rules. Table 1 summa-
rizes steel products we developed in each decade and in each sec-
tor. It is found that above-mentioned eco-products occupy them
more in more recent decade.
3.3. Recycle of city waste in steel plants and utilization of steel plant
waste in city
Waste tires of automobiles reach about 1 million ton a year. 60
thousands ton out of them are recycled in Hirohatas Work for scrap
melting and fuel gas production. In scrap melting carbon content
is used as heat source and hot metal production and steel content
are reused as steel resource. City waist plastics are agglomerated,
charged into coke oven battery and converted to coke by 20% for
iron ore reduction, COG by 40% for hydrogen gas generation and
electricity generation and light oil/tar by 40% for raw materials of
various chemicals (Fig. 3) [3]. On the other hand BF slag is used
as raw materials of cement, which eliminates CO2 emission during
the production of cement by burning limestones. Low-grade waste
heats of steel plants are used for steam supply to surrounding
factories and homes.

3.1. Best available technology transfer 3.4. Process improvements and developments

In addition to these drastic challenging technology develop- Recently new coking process started as proper coke production
ments, a variety of measures for CO2 reduction is under taken. In process in Oita Works. It is called SCOPE21 (Super Coke Oven

400 0.8
Emissions savings (Mt CO2)

350 0.7
Specific savings potential
(t CO2 per tonne of steel)

300 0.6
250 0.5
200 0.4
150 0.3
100 0.2
50 0.1
0 0.0
d

ia

zil

ina

ia
Afr uth

da
Eu CD

US

an

r
he
rl

re
ica

e
Ind

ss
Bra
rai

na

p
rop
Wo

Ch

So

OE

Ko

Ot
Ja
Ru
Uk

Ca

CDQ (or advanced wet quenching) COG recovery Blast furnace

Increased BOF gas recovery Switch from OHF to BOF improvements
Efficient power generation Steel finishing Specific savings
from BF gas improvements potential

Fig. 2. CO2 reduction potential in iron and steel in 2005, based on best available technology transfer [2].
Table 1
Iron and steel products developed to cope with demands in each decade.
Fields 70s 80s 90s 2000s

• Deep-drawing and ironing steel sheets SSPDXTM • EXCELITE (2)
• ZINKLITETM (2)
Automobile
• WELCOTETM (2)
• SILVERALL0Y E (2)
• NS–PACTM steel pipe piling
• High toughness steel for welding
Construction
• Grain-oriented electrical steel sheets • Laser radiation grain-oriented
electrical steels (3)
Electrical machinery and appliance • ALSHEETTM (2)
• Lamellar-tear resistant steel • TMCP steels
Heavy industry and energy
• Wave-shaped plate with
differential thickness
• Plates for nuclear power plant
• 9% Ni plates for LNG tanks
• Hot rolled BH steel
• DP high tensile strength steel
• Various high strength steel
sheets and bars (2) (3)
• Stainless steels for exhaust
manifold (2)
• Fire-resisting steel
• HIPERBEAMTM
• High strength heat treated rail
(2)
• High strength steel wire for
long bridge (2)
• NS column
• NM segment
• Ti cladding steels (2)
• Vibration dumping steels
r
• VIEWKOTE⃝
• Lubricated steel
• High-grade electrically seamed
tube for oil well (3)
• High-efficiency boiler tube and
pipes
• HIARESTTM
• high corrosion resistance
r
stainless YUS270⃝ (2)
• TRIP steels (2) (3)
• Steel tubes for hydroforming
• Pb-free coated sheets for fuel
tanks (1)
• Electrical steel sheets for
hybrid motors (3)
• Ni-contained weathering steel
(2)
r
• HTUFF⃝
• PVC free steel sheets (1)
r
• SUPERDYMA⃝ (2)
• Hyper joint system
• Steel—framed house (2)
• Steel segment for continuous
under ground wall
• Chromate free zinc coated
steel sheets (1)
• Pb-free tin–zinc coated steel
sheets (1)
• Ferritic stainless steel with
high workability
• Thin-gauge high-efficiency
electric sheets (3)
• High-endothermic sheets
r
• New S-TEN⃝ 1 (2)
• HAZ fine-grained steel
• High fatigue strength steel (2)
T. Matsumiya / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 35 (2011) 627–635

• DIS tinplates • New tin free steel • CANLITETM ∗ • Ultra-thin tinplate (0.19 mm)
Container
• TULCTM ∗
629
630 T. Matsumiya / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 35 (2011) 627–635

Fig. 5. Outline of MURC (Multi-Refining Converter) process [5].

Fig. 3. Recycle of waste plastic by charging it into coke oven [3].

1000
Reheating(CDQ)
800
Temperature (°C)

Carbonizing
600
Quenching(CDQ) Quenching
400 (SCOPE-21)
(SCOPE-21)

200 (Conventional process)

Rapid Preheating

0
0 2 4 6 8 10 12 14 16 18 20 Fig. 6. The change in CaO consumption with slag recycling [5].
Time (h)

Fig. 4. Coking time in SCOPE21 [4].

for Productivity and Environmental Enhancement toward 21st

Century) and has been developed in a national project. In this
process coal is rapidly preheated before charging in to traditional
coke oven battery. By this rapid preheating non and weak coking
coal, which has been considered unsuitable for coke production,
can be used as coking coal and in addition coke productivity
becomes 2.4 times of that in conventional process since the total
resident time of coal in coking process is much reduced (Fig. 4) [4].
In steelmaking process the reduction of refining slags con-
tributes materials use efficiency and less emission of unuseful Fig. 7. The effect of deslagging ratio on the total CaO consumption [5].
byproducts. Efficiency of dephosphorization process is aimed by
the use of 2CaO · SiO2 precipitation in refining slags, which can Table 2
contain a large amount phosphor by forming solid solution with Calculation conditions to estimate the effect of deslagging rate on the lime
consumption [5].
3CaO · P2 O5 over complete range of chemical compositions at
steelmaking temperature range, on one hand and MURC (Multi- Hot metal (%) After de–Si, P treatment After de–C treatment
Refining Converter) process has been developed on the other hand [P] = 0.1 Temp. = 1350 °C Temp. = 1650 °C
(Fig. 5) [5]. In this process dephosphorization and desiliconization [Si] = 0.3 [P] = 0.02% [P] = 0.02%
[Mn] = 0.3 [C] = 3.5% [C] = 0.05%
are conducted in the first blow in converter and after that phos-
[Si] = 0.01% [Si] = 0.01%
phorous enriched slag is removed by overflowing where the con- [Mn] = 0.05% [Mn] = 0.05%
verter is inclined while hot metal stays inside the converter. Next, (T.Fe) = 15% (all FeO) (T.Fe) = 15% (all FeO)
the converter is returned its up-right position and decarboniza- (MgO) = 8% (MgO) = 8%
tion and additional dephosphorization is conducted in the second
blow after adding decarbonization slag. After the second blow the It indicates that the unit usage decreases as the removal ratio in-
refined molten steel is tapped through a tapping hole while decar- creases and reaches a saturated level over the 60% in the removal
bonization slag stays inside the converter this time and is hot re- ratio, which is about the half of that in the case of 0% slag removal.
cycled as dephosphorization and desiliconization slag of the next Based on these case studies MURC process have been applied to
charge. In this process, counter flow of hot metal and refining slag proper operation in Oita, Yawata and Muroran Works. Fig. 8 shows
is realized and the unit usage of CaO is much reduced. Concomi- the comparison of unit CaO consumption in various proper opera-
tantly, the amount of slag emitted from steelmaking plant is re- tions in Oita Works [6]. By the application of MURC process without
duced. The effect of the slag removal ratio after the first blow on decarbonization slag recycling, it becomes about 75% of that with-
the unit usage of CaO was case studied under the condition listed out application MURC process and by the application of MURC with
in Table 2. Fig. 6 shows the simulated unit usage of CaO as a func- slag recycling it reaches less than 60% level.
tion of recycling number of decarbonization slag in the case of 60% As the summary of this section, in Japan 10% reduction of
in the slag removal ratio after the first blow. As the recycling num- CO2 emission is aimed by eco-process installations and operation
ber increases, the unit usage of CaO decreases and it saturates after improvements in side steel plants, another 10% reduction is aimed
more than about 5 times of recycling. Fig. 7 shows the unit usage by the cooperation between steel plants and society such as eco-
of CaO at the saturated level as a function of the slag removal ratio. products supply to society, city waist recycling in plants, utilization
 T. Matsumiya / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 35 (2011) 627–635
(Without hot metal treatment = 100%) 120
Total line reduction ratio
100
80
60
40
20
0
Without ORP-M
hot metal
treatment
Fig. 8. Comparison of total lime consumption in various proper operations [6].
of waist slags and heat of plants in society, etc. and another 5%
reduction is expected by the transfer of energy saving technology
to other countries.
4. Application computational thermodynamics
4.1. Control and utilization of nonmetallic inclusions
The control and utilization of nonmetallic inclusions, such as
deoxidation products, are one of the key technology for obtaining
product performance, which is required in steel products listed in
Table 1 including eco-products mentioned in Section 3.3. In order
to optimize steelmaking process for these purposes, computational
thermodynamics is applied.
4.1.1. Solidification path analysis
Solidification path based on Scheil equation can be done dis-
cretely as follows: Some solid fraction is obtained by the equi-
librium calculation at a little bit decreased temperature from the
liquidus temperature in the first step and after discarding the solid
fraction out of the system the next equilibrium calculation is done
for the remaining liquid part at a little further lowered tempera-
ture in the second step. Another some solid fraction is obtained in
the second calculation and this fraction is discarded in the third
calculation at farther reduced temperature. By the repetition of
these with small temperature decrement interval, solidification
microsegregation can be obtained with neglecting buck diffusion
of solute into the solid phase. The increment of solute content in
liquid dCLi (Scheil) during the increment of solid fraction dfS is the
difference of the liquid concentration between two adjacent calcu-
lations. Next, solidification path based on Clyne–Kurz equation [7]
can be realized as follows: By the comparison between Clyne–Kurz
equation, Eq. (1), and Scheil equation, Eq. (2), for microsegregation
prediction,
(1 − ki )CLi dfS = {1 − (1 − 2Ω i ki )fS }dCLi (C −K )
(1 − ki )CLi dfS = {1 − fS }dCLi (Scheil)
the relation between the solute concentration increments is de-
rived based on both equations during the increase of solid fraction
by dfS :
dCLi (C −K ) = {1 − fS }dCLi (Scheil) /{1 − (1 − 2Ω i ki )fS }
where ki is solid/liquid partition coefficient of solute i, CLi is the
concentration of solute i in liquid, fS is solid fraction, dCLi (C −K ) and
dCLi (Scheil) are the increments of solute i concentration based on
631
MURC MURC
Without
slag-recycle
Fig. 9. Relation between fraction solid and temperature obtained in solidification
path analysis by various microsegregation models [8].
Clyne–Kurz and Scheil equations, respectively, and Ω i is the pa-
rameter which shows the effect of solute back diffusion and de-
fined by Eq. (4).
Ω i = α{1 − exp(−1/α i )} − 1/2 exp(−1/2α i ) (4)
where α is called as solidification parameter and defined as
i
DiS tS /L2 . DiS is diffusion coefficient of solute i in the solid phase, tS is
local solidification time and L is half of secondary arm spacing. By
the adjustment of the solute increment between the calculations
at adjacent two steps the effect of back diffusion is included. An
example of calculated result for Fe–21% Cr–11% Ni alloy is shown
in Fig. 9 [8].
4.1.2. Consideration of nonmetallic inclusion during solidification [9]
The existence of various nonmetallic inclusions is also included
in the thermodynamic equilibrium calculation at every step during
solidification path analysis shown above and it is assumed that
the inclusions are homogeneously distributed between solid and
liquid phases. That is, it is assumed that pushing out of inclusions
by the growing solid does not occur. Based on this assumption the
solute contents of inclusions in the liquid part are proportionally
included in the equilibrium calculation in the succeeding step and
only the increments of the dissolved solutes in the residual liquid
are adjusted by Eq. (3) as mentioned above.
4.1.3. Sulfide shape control in anti-HIC steel for line pipe
When manganese sulfide, MnS, precipitates at spot-like segre-
gation along the centerline in a continuously cast slab for a line
pipe, it becomes film like at the thickness center in a line pipe
and it acts as crack initiation site of hydrogen induced cracking,
HIC. The spot-like segregation is thought to be formed as follows:
The solute enriched residual liquid in the inter-dendritic region is
squeezed out due to solidification shrinkage or slab bulging and
(1) entrapped in a spot-like form along the centerline of slab. In order
to prevent from MnS precipitation, Ca is added in anti-HIC steels
(2) so that sulfide changed from MnS to CaS (calcium sulfide). That
is, sulfide shape control is targeted. However, MnS precipitation
cannot be prevented when the size of spot-like segregation ex-
ceeds a certain diameter even if the Ca is properly added to the
steel. The average chemical compositions of anti-HIC steel for line
pipe is listed in the first line in Table 3 and the chemical composi-
(3) tions of a spot-like segregation is listed in the second line which is
equivalent to the solute concentration in the inter-dendritic resid-
ual liquid at dendrite fraction solid of 0.90, which is calculated and
validated by the observation in the slab. The coupled precipitation
model was applied to analyze the chemical compositions change
632 T. Matsumiya / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 35 (2011) 627–635
Table 3
Chemical compositions of anti-HIC steel on average and in the residual liquid of growing dendrite at fraction solid of 0.9 (calculated value) [10].
(%) C Si Mn
Average 0.081 0.16 1.02
CL90 0.317 0.218 1.32
CL90 : Salute content in liquid phase at fs = 0.9 obtained by Clyne–Kurz equation (L = 200 µm, ts = 200 s).
Fig. 10. Changes of the amount of dissolved solutes (a) and nonmetallic inclusions (b) in the residual liquid during solidification of a spot-like segregation with a diameter
of 100 µm (calculated values) [10].
of nonmetallic inclusions during the solidification of the spot-like
segregation. Fig. 10 shows the result when the spot-like segrega-
tion is 100 µm in diameter. At the beginning of the solidification,
oxygen is trapped as CaO–Al2 O3 almost completely and dissolved
oxygen is less than 1 ppm. The rest of Ca is used for capturing S
as CaS and dissolved Ca is about 0.01 ppm. Dissolved Al is about
200 ppm and dissolved S is about 70 ppm. As solidification pro-
gresses segregating sulfur decomposes CaO in CaO–Al2 O3 forming
CaS. Dissolved Al captures oxygen from the decomposed CaO form-
ing Al2 O3 . As the result, CaS concentration and Al2 O3 concentration
in CaO–Al2 O3 increase as fraction solid increases. In this case CaO
does not decompose completely throughout the solidification and
segregating sulfur is trapped in a form of CaS preventing MnS pre-
cipitation, that is, sulfide shape control is successful.
When the solidification of a spot-like segregation with a
diameter of 1000 µm is analyzed, the general behavior of chemical
compositions change of nonmetallic inclusions is the same as
that for a spot-like segregation with a diameter of 100 µm as
shown in Fig. 11. However, CaO decomposes completely at the
very end of solidification. This is due to less effectiveness of back
diffusion of sulfur because of the larger diameter of the spot-like
segregation and segregating sulfur consumes CaO more rapidly.
After that there is no source of Ca which captures segregating S
and as the result MnS precipitates, that is, sulfide shape control is
not successful in this case. These calculations were done by both
analytical method [10] and discrete method [9]. Fig. 12 summarizes
P S Al Ca O
0.0050 0.0012 0.0290 0.0033 0.0025
0.0203 0.0090 0.0447 0.0270 0.0270
the result of calculation for spot-like segregation with various
diameters. It indicates that MnS precipitates when the diameter
of the spot-like segregation exceeds 300 µm. Fig. 13 shows the
relation between the observed Mn peak concentration in a spot-
like segregation and its diameter. Mn peak concentration step-
wisely increases when the diameter exceeds 260 µm, which is due
to the MnS precipitation in the spot-like segregation. The threshold
value agrees well with the calculated results with the coupled
precipitation model. In order to suppress the MnS precipitation,
the diameter of spot-like segregation should be regulated as well
as proper addition of Ca, which can be done by minimizing
slab bulging and applying soft reduction of slab thickness to
compensate solidification and thermal shrinkage.
4.1.4. Oxide inclusion control in austenitic stainless steel for wire
drawing
The inclusions in an austenitic stainless steel for wire drawing
should be deformable during the wire hot rolling. Otherwise wire
breaking occurs at the hard crystalline phases in the inclusions
during the process. The coupled precipitation model is also applied
to control the oxides inclusions in this steel whose chemical
compositions are listed in Table 4 [11]. Fig. 14 shows the calculated
Al2 O3 and SiO2 concentrations as functions of fraction solid and
total oxygen content in the steel by the use of coupled precipitation
model. The calculated concentrations at the fraction solid of 0.5
agree well with the experimentally observed ones. The increase
of total oxygen content from 40 to 80 ppm sharply decreases
 T. Matsumiya / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 35 (2011) 627–635 633

Table 4
Chemical compositions of the austenitic stainless steel in mass% [11].
Cr Ni C Si Mn Al O Mo Ca Mg

18.3 10.35 0.02 0.5 1.1 0.0015–0.0030 0.0040–0.0150 0.01 0.0005 0.0004

Fig. 13. Mn peak composition as a function of the diameter of spot-like segregation

(observed) [10].

Al2 O3 concentration and sharply increases SiO2 concentration,

Fig. 11. Calculated change of amounts of nonmetallic inclusions in the residual
liquid during the solidification of a spot-like segregation with diameter of
1000 µm [10].
which may change the nature of the oxide inclusions. However,
further increase of total oxygen does not change Al2 O3 and SiO2
concentrations so much, that is, the nature of inclusions. The
increase only increases the amount of inclusions.
By the use of thermodynamic equilibrium calculation the
liquidus temperature of inclusions and fractions of various
crystalline phases appeared in the inclusions at the various
temperature can be obtained [12]. Fig. 15 compares the calculated
fractions of every phase in oxide inclusions at various temperatures
in the stainless steels with total oxygen content of 40 and 80 ppm.
In the inclusions in the steel with total oxygen content of 40 ppm,
hard crystalline phases such as Al2 O3 and spinel MgO·Al2 O3 occupy
large portion even at high temperature of 1600 °C. These inclusions
are considered to be undeformable. On the other hand, in the
inclusions in the steel with oxygen content of 80 ppm, liquid
phase occupies 80% even at the low temperature of 1200 °C.
These inclusions are considered to be deformable. According to
this finding an austenitic stainless steel for wire drawing was
successfully developed.

4.2. Optimization of demanganization process

In order to optimize various refining processes including MURC

Fig. 12. Fraction liquid and temperature at MnS precipitation and temperature
at fraction liquid of 0.999 as functions of the diameter of spot-like segregation
(calculated) [10].
process, computer simulation of the processes are conducted
mainly by the combination of fluid dynamics and computational
thermodynamics analyses. The refining of steel is conducted
mainly by the use of slag/metal reaction and injection metallurgy.
In both cases chemical reaction occurs between liquid metal and
refining agents that are frequently liquid oxides. The slag/metal
refining process can be analyzed by coupled reaction model
developed by Robertson et al. [13]. The reaction between injected
flux and metal can be analyzed in the same manner. Fig. 16 shows
the schematic view of the model. In the model, thermodynamic
equilibrium for each component oxide in the slag and solutes
634 T. Matsumiya / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 35 (2011) 627–635

100

100
Al2O3 concentration (wt%)
80

80
SiO2 concentration (wt%)
60

60
40

40
20

20
0

0
0 50 100 150 200 0 50 100 150 200
oxygen content (ppm) oxygen content (ppm)
(a) (Al2 O3 ). (b) (SiO2 ).

Fig. 14. Alumina and silica contents in inclusions as functions of total oxygen content [11].

100 100
90 90
80 80
70 70
wt% of phases

wt% of phases

60 60
50 50
40 40
30 30
20 20
10 10
0 0
1100 1200 1300 1400 1500 1600 1700 1800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
temperature (°C) temperature (°C)
(a) [O] = 40 ppm, fs = 0.5. (b) [O] = 80 ppm, fs = 0.5.

Fig. 15. Calculated fractions of various phases in inclusions at various temperatures [11].

in metal is assumed at slag/metal interface and double diffusion FeO CO

layers are considered along the slag/metal interface. Chemical
compositions in the bulk metal and the bulk slag outside M1aOb C
the boundary layers are treated as uniform with respective M1
concentrations. Concentrations in slag and metal at the slag/metal
interface are calculated by the use of flux conservation equations M2cOd O
of metal components and oxygen across the double boundary
M2
layers and thermodynamic equilibrium equations for component
oxides with solute contents in the metal at the interface. In the
case of carbon (C), a rate equation of carbon monoxide (CO)
evolution is applied at the slag/metal interface instead of the local
SLAG METAL
thermodynamic equilibrium, C + O = CO, and a mass balance INTERFACE
equation for C between C flux from the metal and the CO evolution
rate is considered. Fig. 16. Schematic diagram of the coupled reaction model.
Once the interfacial concentrations are determined, the flux
of each metal component and oxygen from the bulk metal to potential in the powder is not enough to oxidize manganese
the bulk slag, or vice versa, as well as the CO evolution rate in hot metal after the manganese oxide reaches its maximum
and decarburization rate are obtained and chemical composition and manganese oxide is reduced back to hot metal. Therefore,
changes in both the bulk slag and metal are calculated. from the viewpoint of efficient demanganization the injected
This model was applied to optimize demanganization process powder is desired to float up to the top slag when the manganese
of hot metal, where iron oxide powder is injected in a hot metal concentration in the powder reaches the maximum. Since the
through an immersed nozzle [14]. The chemical composition time at the maximum manganese concentration becomes longer
change of the injected powder is analyzed with the model. The as demanganization process proceeds due to less concentration
results are shown in Fig. 17. Silica concentration increases and iron in silicon and manganese in hot metal, the depth of nozzle
oxide concentration decreases monotonically, while manganese immersion should be increased accordingly to realize efficient
oxide concentration reaches its maximum and decreases as time demanganization. According to this result, the demanganization
elapses after the powder is injected. This is because oxygen process is operated successfully.
 T. Matsumiya / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 35 (2011) 627–635
FeO, SiO2, MnO (wt%)
(a) Beginning of operation
Time after injection (sec)
FeO, SiO2, MnO (wt%)
(b) Middle of operation
Time after injection (sec)
FeO, SiO2, MnO (wt%)
(c) End of operation
Time after injection (sec)
Fig. 17. Chemical composition changes in the refining powder after it is injected
to hot metal in demanganization and desiliconization process [14].
5. Concluding remarks
In the first half, firstly the activities in COURSE50 program,
CO2 Breakthrough Program in Japan, was explained, which mainly
consists of CO2 separation from BFG, hydrogen gas generation from
COG and iron ore reduction of hydrogen gas. Secondly, incremental
reduction program of CO2 emission is explained, which includes
the transfer of best available technology of CO2 emission reduction,
the supply of various eco-products including high strength steel
sheets and plates and high performance electrical steel sheets
for energy savings in society, recycle of automobile tire and
city waste plastic in steel plants, utilization of BF slags and
waste heat in society and improvements and development of
steel processes for less emission of CO2 . In the second half
examples of utilization of computational thermodynamics for the
development of steel products including eco-products and more
environment friendly steel processes. They are for the control and
utilization of nonmetallic inclusions and optimization of hot metal
demanganization process.
635
In addition, as concluding remarks the author would like to
point out the followings from other viewpoint: Sectoral approach
proposed by IISI (presently, WSA) should be followed instead
of cap and trade for the reduction of CO2 emission. When the
environmental tax is to be introduced it should be put on the
products on sale based on the LCA figures, that is the amount
of CO2 emission. When some products are produced with special
care for less emission of CO2 gas, which can be verified by
putting eco tag, the amount of the environmental tax is reduced
accordingly. Other wise the tax amount is determined based of
default values of LCA. In this circumstance, the products, which
are produced with less emission of CO2 gas under special care,
have better competitiveness in the market, which encourages the
selection of environmentally friendly products to the consumers
and concomitantly the environmentally friendly production to the
manufacturers.
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