ISIJ International,

Vol.

35

(1

995). No. 12, pp.

1477-1482

Effect of the

Composition

of

Oxide on the Reaction between Oxide

of Steels

and Sulfur during Solidification

Hiroki

K ) and GOTO. en-ichi MIYAZAWA Tetsuji KADOYAI

Kimitsu, Kimitsu, Chiba-ken, 299-1 J~pan, Kimitsy, Chiba-ken, 299-1 Japan.

Kimitsu R&D Laboratory, Nippon Steel Corporation, 1) Kimitsu Works, Nippon Steel Corporation, Kimitsu,

(Received on March 29. 1995. accepted in

final

form on

May26.

7995)

the effect n order to elucidate the reaction between oxides and sulfur in molten steel during solidification, of composition of oxides in continuously cast steels has been observed and analyzed, The results obtained are as follows.

CaO-SiO.-Al203 and CaO-SiO, oxides are observed in low Al content steel (Al=0.005mass'/o) and CaO-Al.O, oxides are observed in high AI content steel (AI =0.031 masso/). CaO-SiO.-Al.O* and CaO-Al,03
than CaO*SiO. oxides. High S content in oxides was obtained with high capacity of oxides at the solidification temperature of the steel. Because desulfurization by oxides which have high sulphide capacity and high liquid fraction occurs during solidification, Ssegregated in the center of slab is absorbed by the oxides.
oxides have higher
liquid

fraction

and high

Scontent

sulfide

solidification; KEYWORDS:

oxide; deoxidation;

precipitation;

calcium; sulfur.

l.

Introduction

Utilization of oxides in steel as heterogeneous nucleation sites of transformation is and precipitation

effective

the mechanical properties of steel. Oxide where is precipitated is effective for fine steel. Concerning the precipitation structure of of varies on oxides, it is shownthat the precipitation of with the compositions of oxide,1)

methodto control

an

MnS

MnS MnS
in
steel,

content on the oxide composition. The slab obtained was cut in the direction of slab thickness. The numberand size of oxides were measured magnification, and the by an optical microscope by I OOO chemical composition of oxides wasanalyzed by EPMA. The size of oxides measuredranges from to 20 ~m. The re]ationship between oxides and sulfides wasobserved by

On the

CMA.8) The stablest

contrary,

MnS, precipitated

solid-phase and liquid-phase components

singly

of crack. It is important to prevent can be initiation the formation of MnSfor plate and linepipe steels.2) Howeverthere are manyreports on the precipitation of MnSand CaSand the dissolution of CaS in calcium aluminate,37) there are less information on relationship between Sand oxide. The composition of oxide is to assumed have a large infiuence on the reaction between the oxide and sulfur during the solidification of steel. In this study the effect of oxide composition the reaction on between oxide and Sin the steel during solidification of steel has been investigated.
2.

of oxides at a given temperature and the amounts of oxides were calculated by using SOLGAXMIX.9) The change in the composition of molten steel during the solidification was calculated by using the modello) of oxide precipitation that takes into account of microsegregation. The activities of oxides in the calculations were estimated by using the cell model and parameters of Gaye and Welfringer.11) The values used by Yamada et al.10) in their calculation of composition of inclusion during the solidification were adoptd as the standard formation free energy of oxides and the interaction coefficient of elements in the molten steel.
3.

Experimental Procedure
Al,
Si

Experimental Results

deoxidizers to steel during tapping from BOF. After the addition of a flux

and

Mnwere added as

Table
Table

2 giveS
1.

the chemical compositionS Of oxides in

of compsoed

and CaO CaF2With Ar

blowing at about

l 580'C in the secondary refining process, the steel was thick slab and used as continuously cast into a 240 test material. The chemical compositions of test steels with different are given in Table l. Steels I and Al contents were used to investigate the effect of Al

Chemical compositions ofspecimens cut from the continuously cast steel slabs. (mass'/,)
Sl

mm

No.

C
0.04 0.04

Mn
1.34

P
0.004 0.006

Al

O
0.0020 0.0019

Ca
0.0023 0.0020

>

0.15

0.26

1.26

0.0005 0,004 O.O003 0.031

477 1

C 1995 ISIJ

ISIJ International,

Vol.

35 (1995), No. 12

Table

2.

Chemical compositions of oxides

(masso/o)

in

low Al

steel.

No. A- i A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9

B- l B-2 B-3

CaO Al203
43.3 44.7
12.7

Si02
23.8

MnO MgO
0.2 0.6
6.

FeO
7.8

S
l.l

14.4

l 49. l
54.

l5.6
15.l

l .3 21
23
.

4.7

6.0 2.9

2.0

22.3

58.l

2.5
19.l
.6 1 .2 1

49.3 60.6 53.5 55.3

46.

23

.3 31 l .3 31 34. l
.

l O. l
O.

l .6
3,4
0.7

0.2

(C 1)
Fig.
l.

t--l

lOpm

(C 7)

4.0
2.2 7.7
3.l

0.4
0.2 0.4
0.8

0.0 0.2
O,

2.4
0.8 0.3
1.5

Morphology of an oxide (C-1) mainly composedof and an oxide (C-7) mainly composed of CaO, Si02 and Al203 in low-AI steel.
and CaO Si02
~~~oo

12.3
19.5

20.5

0.6 0.2

5.7

o.2 0.9 0.3

6.3
3.5

10

54.5 57.8 45.6 51.5 62.2 64.2

54.8

0.9 0.9
13.5

22.9 34.8
35.2 25.2 32.6 22.4
19.9

B-4 B-5 B-6 B-7

-l C- l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C- IO C- Il C- 1 2 C- 1 3 C- 1 4 C- 1 5

l l o. ~ O. l
O. O.

2.9

l .9
2.2
5.

2.6 2.6

0,0

3.0
5.7

0.4
3.5

0.5

2.8

0.2
0,0 0.4

0.6 0.2
l.2

7.7 2.8

l 1.2 l .5
l,l
.2 1

l l .8 O. l O. l O. l
O,

o 7 ~6
~2
>

~8 E
o e o

co9

58.2

54.4 52.3 50.8 60.3 55,3

38.5 34.8 36.0

.2 31

2.4
3.8

O.

l O. 1
O.

2.8

O.O
0,3

7.0
5.5

2.6
6.7

0.6 0.7 0.9

13.2

0.2
O. O,

0,4
O,

38.2
32.3

51

.O

1 1
l0,7

,6

6 21
20
.

l l O, l
0,3

2.7
.6 1 l .O l.l

3,0
3.0
6,

1 l 1
Fig.

(/)

0,0 2.9
2.
6.

5 4 ~ 3 ~ 2O c 8 1o o
o
a)

e
C
60

(s~rface)

(c*~ter)

20 1

.9

7.7
5.5

57.4 58.3 50.8

49.

14.7

14.6
18.9 16.9
18.3

17.7

l O. l
O.

Distance from slab surface (mm)

2.

0.3
.2 1

4.4
2.5 6.7
2.8

3.5

26.5 22.8
22.

O,3
O. O.

0.7 0.9
3.3

4.2
3.0

Changein

Scontent

with distance from slab surface.

49.7 54.6
.2 51

I l l

16.9

23 .4
28.6

0.0
O,

l .5
3.8

l ,8
0,4 0.8

(mass%)

2,9 7,8

Al S Mn
2
[:

6.6

from slab surface A- : 4mm B- : 60 from mm slab surface from slab surface C- : 120

:_
(slab center)

l
S

h--1 51lm Mn

mm

measuredby the EPMA. n oxide A mainly composedof CaO and Si02 and another oxide of mainly composed CaO,Si02 and Al203 were observed in the low Al steel. The morphologies of these oxides are shown in Fig. 1. Each oxide is spherical. These oxides were located in the center of the slabs. The measurementsshowedthat Scoexisted with the oxides and that the pure CaSwhich did not coexist with oxide were not observed.
the low A1 steel

Fig.

3.

Chemical compositions of an oxide (C-1) mainly and Si02 in low-AI steel. composedof CaO

CMA
slab

The Scontent of oxides in the direction of the thickness was investigated. Because S content is

enriched in the center segregation zone of the slab, the reaction between the oxides and the solute elements in the residual molten steel is assumedto becomenoticeable. The content in oxides in the center segregation zone was comparedwith that of oxides in the surface from the slab surface) and a quarter thickzone (4 from the slab surface). The center ness zone (60 segregation zone is defiend as the central area of the slab is segregated to in the thickness direction where a of more than .3 times as great as the mean content content of steel.8) The contents of oxides in the surface, a quarter thickness and center segregation zones are and shownin Fig. 2. CaO-Si02-A1203 CaO-Si02bxides

each zone. Almost all oxides in the surface and a quarter zones have low Scontents of l mass*/, or less, while oxides with Scontent of 2mass"/. or more were observed in the center zone. The oxides observed in the center segregation zone can be classified into the CaO-Si02 and the CaO-Si02Al203 type. The elemental distributions of the CaOSi02 and CaO-Si02-Al203 oxides are shownin Figs. 3 and 4, respectively. The CaO-Si02oxide (C-1) contains little S, while CaOSi02-Al203 oxide (C-7) contains about 2mass~/o of S. The two oxides are greatly different

were both observed

in

in

mm

mm

Mn

content. Since content was different with the type of oxide, the composition of oxides was invetigated for its effect on the content in oxides. The CaO/Si02 ratio ranged from .4 to 2.0 for the CaO-Si02oxides observe in the low Al steel, and the CaO/Si02ratio and Al203 content ranged from .9 to 3.9 and from to 20 masso/o, respectively, for the CaO-Si02-Al203 oxides observed in the low Al steel. As shownin Fig. 5, content increases with increasing A1203content. This tendency is noticeable in

C 1995 ISIJ

1478

ISIJ International,

Vol.

35

(1

995), No.

12

Al (mass%)
5
4

Al

~~OO

10

a) u) co a) a)
>

3
2 l

S Mn (mass%)
3
2
l

~
t-l 5/Im
S
io

6
4

o
~'

o
Fig.
4.

o_

Mn
Fig.
6.

o ~ o o (/)

9 8 7 6 5 4 3 2 1

(Slab center)

slab 120mmfrom

surface

from slab C 60mm slab surface from surface O4mm

e o

oe ~)d'
o

Chemical compositions of an oxide (C-7) mainly of composed CaO. Si02 and Al203 mlow-AI steel.
~

o O 1

CaO/Si02Of oXides
CaOISi02 and

CC 3 4

5
of

10
(Slab center)

Relationship between oxides in low-AI steel.

3.

Scontents
high Al
steel.

~
(D (D :~

~9 E8
O

from 20mm slab 1

surface

Table

:9

~ q) ~
(/)

O O

30 O 1 O 20 Al203 COntent in oXideS(maSSo/o)

0.4
Fig.
5.

6 5 4 3 2 1 o

from slab surface C 60mm slab surfaoe from o 4mm e

Chemical compositions of oxides

(masso/.)

in

No.
C- l C-2 C-3
20 C- : 1

CaO Al203
56.7 48.5 52.3

SIO
0.9

MnO MgO
I I O, 1
O. O,

FeO
2.7

S
.O 1 .O 1 .6 1

ee e~)

o o

39.0 40.3
34,

0.6
0.6 4.0

1I
.

4.2
.6 3

0.8

from mm slab

surface (slab center)

SiO,

Relationship between Al203 and

in

low-AI

steel.

Scontents

of oxides

O6
0.5

S content
0_O

~ 1.0

in oxide

ETass%

1.0 mass%

0.5
~e'
~;-

the oxides in the center segregation zone (e). In the center segregation zone, the content tends to increase with increasing CaO/Si02 ratio as shownin Fig. 6. The content of oxides changes with the composition of oxides in the this way. Table gives the chemical compositions of oxides in the slab center zone of the high Al steel as determined by the EPMA. he oxides mainly consist of CaO T and Al203, and have contents of about mass"/*. In order to clarify the relationship between the chemical composition and content of oxides, the chemical compositions of oxides observed in the slab center zones of the low A1 steel and high Al steel are

O o.

0.4 ~~

0.7
o.

O
l\o

Oll

~l O. O

~ l O,

~. lb

0.3

~- Low-Al

stee l

0.2
0.1

0.9

CaO
Fig.
7.

o,1

~
0,2
.3

High-AI steel
0.5

0.4 NAl203

0.6

Ala03

Chemical compositions of oxides Si02 system,

in the

CaO-AI203-

shownon a CaO-Si02-Al203 ternary phase diagram in The low Al steel has CaO-Si02oxides (indicated by the symbol O) that contain little A1203 and is low in S and CaO-Si02-Al203 oxides is high in S. The CaO-Si02-Al203 oxides (indicated by the symbol O) that are high Al203. The oxide with high Al203 content is high in S. The CaOSi02-Al203oxides (indicated by
Fig. 7.

with oxide wasnot observed, that the oxides in the center segregation zone have a higher Scontent and that the S content of the oxides changed with the chemical composition of the oxides. The reaction between the oxides and in the molten steel during the solidification of steel
is

the symbol masso/, or

O) observed in the high A1 more of S.

steel

contain

discussed as follows.
Effect of Chemical Composition of Oxides on Reaction between Oxides and in Molten Steel

4.1.

4.
It

Discussions

has been found that the

CaSwhich does not

coexist

Judging from the finding that the oxides in the center segregation zone have a higher Scontent as shown in

T479

C 1995 ISIJ

ISIJ International,
it is more reasonable to assumethat the segreacts with the oxides regated during solidification rather than that the reacts with oxides in the molten steel. This can be explained as follows. Spot-1ike segregation at the center can be predictable by analysis on the assumption that the molten steel is globularly contained between the dendrites when the calculated by using the solid fraction is 0.9.12) When oxide precipitation modello) that takes into account of the content between segregation during solidification, the dendrites is found to be 0.0038masso/o for the low Al steel whenthe solid fraction is 0.9 and about times content of the molten steel. Since as great as the initial more reacts with the oxides in the center segregation content of the oxides observed in the center zone, the segregation zone is estimated to be higher than that of the oxides observed in the surface and a quarter thick-

Vol.

35 (1995), No. 12
l O~
90 a~ 80

Fig. 2,

MgOA1203 '
CaOAl 203

O >
aQ Q) u~
C:,

7~
62) 5e)

Liqu id
~~:~~~~~~l//'

.::

,~

eH 40

O O +. U
~::
,T'~

30
Z~)

~~~~~~~3cao_'Si02

~~

IQ

2CaOSi 02
9~e]

e08

1~~O Ilee

lzoo

13G)G I~o~i

Is~]o

Temperature( 'C
Fig.
8.

160~ 17~0

Fraction

of equilibrium
in

Si02-Al203 oxide
temperature.

phase of the (C-7) CaC~ low-AI steel with changing

ness zones. In order to clarify the changein the content in oxides molten state with the chemical composition of oxides, phases) and ~) (solid, Iiquid, and solid-liquid of oxides sulfide capacity of oxide are discussed as to their effects. First, the molten state of oxides is discussed. When oxides react with molten steel, Iiquid oxides, solid oxides, and solid-1iquid oxides are assumedto be different in reactivity. The liquid fraction of oxides at the solidi-

~~OO

10

9 E8 ~7 O ~ 6 O 5
Cl)
'~>

U) U) (O

O CaO-Si02-AI203 O caO-Si02 o O o Gp o o

e caO-Al203

fication

temperature of
its

steel

gated for The liquid

relationship with the content in oxides. fraction of oxides at the steel solidification temperature is more accurately determined by calof multicomponent oxides by culating the precipitation rather than estimating from the phase SOLGASMIX6) diagram of CaO-Si02-Al203' The oxides were assumed oxides, exto be CaO-Si02-Al203-MnOMgO-FeO cluding S. The calculated results of the oxide (C-7) in the Table are shownin Fig. 8. When temperature of oxides reaches the liquidus temperature of oxide, 2CaO

was obtained and investi-

~*

~'
(/)

O O O

3 2 1 O O

~)8
fraction

oe e
1
in

0.5

Liquid fraction

of oxides

Fig.

9.

Relationship between liquid oxides at 1527'C.

and Scontent

Si02 precipitates,
precipitate

and various equilibrium

phases then

as the temperature decreases. The liquidus temperature of the low Al steel is calculated to be 527'C by the equation of Hirai et al.13) The liquid fraction of the CaO-Si02Al203 oxide (C-7) at the liquidus

sorption from the gas phase to the slag (oxide) phase represented by Eq. (1). The sulfide capacity C, that indicates the ability of slag to absorb according to Eq. (1) is defined by Fincham and Richardson,14) as given
is

by Eq.

(2).

olo. temperature of the low Al steel is estimated at 79 This method was used to obtain the liquid fraction of

CaO-Si02, CaO-Si02-Al203, and CaO-Al203oxides. The relationship between the liquid fraction and S content of these oxides is shown in Fig. 9. The CaOAl203 oxides (indicated by the symbol e) are liquid and contain about I masso/o of S. The liquid fraction of the CaO-Si02-Al203 oxides (indicated by the symbol (~)) increases, ranges from 0.6 to 1.0. As the liquid fraction the Scontent increases. The effect of the liquid fraction is recognized. on the reaction between the oxides and S The liquid fraction of the CaO-Si02 oxides (indicated
by the symbol O) has little
the

l S2(g)+02~(slag)=S2~(slag)+ 2
C.
(masso/oS) P~~2
'

02(g)

......(1)

.......(2)
....

p~~2

where,

content, and the content of less than 0.5 masso/o. It was found that the liquid fraction of oxides in the solid-1iquid phase at the CaOSi02Al203 the steel solidification temperature infiuences the reaction
effect

on the

CaO-Si02 oxides each have

equilibrium partial pressure of oxygen equilibrium partial pressure of sulfur content of slag. ratio Ls between the slag and the distribution When is used concerning the steel (=(o/oS)/[o/oS]) molten equilibrium reaction of between the slag and molten steel as expressed by Eq. (3), the sulfide capacity C, of Eq. (2) is represented by Eq. (4).
P.2 : P*2 : (massoloS) :

=S2~+0 S+02~
C*

...........(3)
.........

= L*

between the oxides and the

Sulfide

capacity of oxides

Sin
is

the molten steel. studied as follows.

where, a~ :
f.

activity activity

Ab-

""" of oxygen in molten steel coefficient of sulfur in molten

'

(K*lK.)

'

(a.Ifs)

"""""'(4)
steel

C 1995 ISIJ

1480

ISIJ International,

Vol.

35

(1

995). No.

12
is

K* :

equilibrium constant of reaction in which l/2mol of S2 gas is dissolved in molten

steel

When oxide an

present in the solid-liquid

phase,

K~: equilibrium constant of reaction l/2mol of 02 gas is dissolved

steel.

in
in

which molten

content of the solid portion of the oxide is assumedto be by far lower than that of the liquid portion of the oxide. For this reason, Scontent of liquid oxides is estimated by Eq. (9).
(masso/oS)Liq.

K* and K. in Eq.

(4) are calculated

as given

by

= (masso/oS)~b~./,fLiq.

(9)

l/2S2(g)=S (masso/o)

.......................(5)

where, (masso/oS)Liq.:
(6)15)

S content
oxide

of liquid

portion

of

logK*=6535/T-0.964
ll202(g)

................

= O(masso/o)

......................(7)

logK~=6 135/T+0.178
If the activity

(8)16)
................

in the

molten

steel are constant,

of oxygen and the activity coefficient of C* becomesan index

is of the degree to which S distributed

betweenthe molten

steel

and slag

(oxide).

Since the oxides in the low A1 steel are in the solidliquid phase at the steel solidification temperature as shownin Fig. 9, the sulfide capacity of liquid portion of oxides is calculated here. The compositions of the liquid The oxides were calculated by the SOLGASMIX.9) analysis values of the oxides in Table and the liquidus tempeature of 527'C were used in the calculations. Figure 10 shows the values of sulfide capacity of

: measuredScontent : Iiquid fraction of oxide. The sulfide capacity C.1 of each oxide is obtained by using the S contents of the oxides shownin Tables 2and and Eq. (9), the S contents of 0.0038 and 0.0023 masso/o 3 in the center segregation zones of the low Al and high Al steels, respectively, and Eqs. (6) and (8), and by assumingf*= I and a~ = 0.0001 The sulfide capacity values shown in Fig. 10 were measured by Ficham et al.14) at 1650'C and must be extraporated for the steel solidification temperature of l 527'C in this study. Hino et al.17) measuredthe sulfide
(masso/oS).b~.
fLiq.
.

CaO-Al203-Si02

slag

measured by Fincham and

550'C, C* of CaO-Al203 binary oxides at close to the steel solidification temperature in this study, and at 650'C. The sulfide capacity C*2 of each oxide is estimated by assurning that the temperature dependence of the sulfide capacity in the temperature
capacity

which

is

Richardson,14) and the compositions of liquid oxides in the low A1 and high Al steels. The oxide composotions
content. The CaO-Si02 are shownas classified by the oxides are low in the sulfide capacity. As the A1203 content and the CaO/Si02ratio increase to change from the CaO-Si02 oxides to the CaO-Si02-Al203 oxides, oxides in the sulfide capacity increases. The CaOA1203 the high Al steel have such a high sulfide capacity as the CaO-Si02-Al203 oxides. of between the In order to evaluate the distribution oxides and the molten steel by using the sulfide capacity,

range of 1550 to 1650'C is an sameas at 1527'C and extraporating the logC*-1/T relation to 1527'C. The relationship between the sulfide capacities C*1 and C*2
is

shown in

Fig. 11.

The sulfide
each other,

capacities

almost agree with

C*1 and C*2 and CaO-A1203and

the sulfide capacity C*1 of the oxides in this experimental study is estimated.
Si02

Whenthe sulfide capacity C*1 rs obtained based on the assumption about the oxygen content, it is close to the sulfide capacity C*2 extraporated from the experimental data of Fincham and Richardson.14) This confirms the validity of the assumption. The effect of the liquid fraction of oxides is recognized in oxides with high sulfide capacity (CaO-Si02Al203 oxides). The oxide with low sulfide capacity (CaO-Si02 oxides) is low in S, so that they do not have the effect of the liquid fraction. The sulfide capacity and melting
content.

oxides with high S CaO-Si02-A1203 content are higher in sulfide capacity than CaO-Si02 oxides with low S

0.4

'21>

0.6 0.5

0.5
7>

.6>

C ~ 1.0 l.o O
0.4

content in oxide mass% mass%

~
co

g:

c DI
J:2.~as

~e'
o.

q)

O. 6(

~
tP,

> 10~2

C caO-Si02-Al203 O Cao-Si02
_

e caO-Al203

7 O

-O

1~

~:

0,3

~ E
o *
(D
(~s

C
10~3

C8 C
C

o.

~O

~
4 2
l)

~
C

O2
.

~)

0.9

0,l

o CL
co
>

OO

e)

f*;~0.5

CaO
Fig.

0.1

0.2

Q~0~

0.4 NAl203

0,5

O6

Al203

O I 0~4 0~4
Fig.
Il.

a)

lO.

Sulfide capacity in the

CaOAl203-Si02systern.

1Csl calculated0~3 1 with

10-2
the experimeta] data

C* measuredby Fincham et a/.14) >: value of C* in x l0-4 o, O: this study

Comparison of C*1 by the present work with c*2 extraporated from that by Fincham et a/.*")

1481

C 1995 ISIJ

ISIJ Internationa],

Vol.

35

(1

995). No.
Table
4.

12
data Thermodynamic
for the calculation.

point affect the

4.2.

Scontent

in oxides.

Reaction between Oxides and during the Solidification

S in

Molten Steel
steel
is

Si

Mn+0=MnO
2Al+3Q=Al203

+ 20 = Si02

The reaction between Ca and

described by Eq. (lO)

S in

molten

~~+~:=CaO

.OI 35 AG' = - 1 492 + 51 T "= AG -70389+31.33'T '= AG -266282+82.72 T

'

(cal/mol)1 1'l 5) (cal/mol)11'15) (cal/mol)1

1'15) 1'16)

AG"=-

150796+34.65T (cal/mol)1

~~+~~>(CaS) ........
The content of
dissolved

..........(10)
is

Ca in

the molten steel

estimated as follows. the When content of dissolved Ca during the solidification of steel is calculated during the oxide precipitation modello) with the equilibrium data of Table 4, the at Ca contents are 2x l0~3 and 5x 10~3ppm a solid fraction of and 0.8 respectively and are extremely low as comparedwith the observed Ca content of steel. Assuming that the oxygen in the steel is present as oxides, the Cacontent as oxides in the steel is estimated from the measuredoxygen and Cacontents by Eq. (1 l).

capacity and liquid fraction. (2) To control oxide to a high sulfide capacity composition is found to accelerate the desulfurization of steel by oxides during solidification and to encourage the absorption of segregated by oxides in the center segregation zone of slab.

Acknowledgments The authors wish to thank Professor NobuoSano of the University of Tokyo and Dr. Hiroyuki Kajioka, advisor of Nippon Steel Corporation for their valuable guidance and discussions on this study.

[Ca] as ~**d* ={[O]/(O).

.

** .**d*
.

(Ca)i...id.

......(11)
l)

REFERENCES
M. Wakoh, T. Sawai and
(1992), 1687.
2) 3) 4)
5)
S.

where, [Ca]as

[O] : Ocontent in steel (O) i* .*id* : Ocontent in oxide (Ca)i* .*id. : Ca content in oxide. The measured contents in Table I were used for [O], and contents measuredby the EPMA used for were (O). and (Ca) i* ~*id*. [Ca]as 'xtd* in the steels I and ** ~**d* are calculated to be 28 and 24 ppm, respectively, and and , are relatively close to [Ca]~bs in the steels respectively. This meansthat most of the Ca is present as oxide and the dissolved Ca content is extremely low. It is found that the reaction expressed by Eq. (lO) does
,

'^id'

: Ca content

as oxides in steel

Mizoguchi: Tetsu-to-Haganb, 78

T. Ototani and Y. Kataura: Calcium Steel: Cleaning and Inclusion

Control, Maruzen, Tokyo, (1981).

S. Kitamura, K. Miyamuraand Y. Fukuoka: Tetsu-to-Hagan~, 73 (1987), 677. O. Shoda. T. Emi, M. Sanbongi, T. Shiraishi and A. Fujiwara: Tetsu-to-Hagan~, 64 (1978), 1538. T. Ikeda, N. Fujino and H. Ichihashi: Tetsu-to-Haganb, 66 (1980),

>

2040.
6)
7)

Koyama,T. Tanaka and M. Kitamura: Tetsu-to-Hagan~, 63 (1977), S161 T. Kawawa, . Imai. T. Usui, K. Taguchi and H. Sato: Tetsu-toR
S.
.

not occur.
It is shown that the desulfurization with .oxide expressed by Eq. (3) occurs during solidification, and that in the oxides greatly depends the the comcontent on position of the oxides.

8)
9)

l O)
l 1)

5.

Conclusions
In order to clarify

the reaction between oxides and in molten steel during solidification of steel, the composition of oxide in continuously cast slabs has been observed. The results are as follows. (1) In a low Al steel (Al=0.005masso/o), CaO-Si02 and CaO-Si02-Al203 oxides are observed. The CaOSi02-A1203 oxides have higher content than the oxides. The content in oxides changes with CaOSi02 their composition. In a high A1 steel (AI = 0.031 massolo), CaO-Al203oxides are observed, and is contained in the CaO-A1203 oxides. The sulfide capacity and liquid fraction of these oxides were estimated. The oxides are found to increase in content with increasing sulfide

l 2) l 3)
l 4) l 5)

Hagani, 63 (1977), Sl61. Y. Ueshima, H. Yuyama,S. Mizoguchi and H. Kajioka: Tetsuto-Hagan~, 75 (1989), 501. G. Eriksson: Acta Chem. Scand., 25 (1971), 265. W. Yamada,T. Matsumiya and A. Ito: Proc. 6th Int. Iron and Steel Cong, Vol. l, ISIJ, Tokyo, (1990), 618. H. Gaye and J. Welfringer: Proc, of Second Int. Symp. on Metallurgical Slags and Fluxes, The Metall. Soc. AIME, New York, (1984), 357. T. Matsumiya, H. Kajioka, S. Mizoguchi, Y. Ueshimaand H. Eska: Trans. Iron Stee! Insl. Jpn., 24 (1984), 873. and M. Hirai, K. Kanamaru H. Mori: Report No. 8837 of 19th Committee on Steelmaking, Japan Soc, for Promotion of Sci.,
(1968).

Richardson: Proc. R, Soc. London A223 (1954), 40. The 19th Committeeon Steelmaking, Japan Soc, for the Promotion of Sci: Steelmaking Data Sourcebook, Gordon and Breach
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C. L,

W. Fincham and F. D.

l 6) l 7)

Science Publishers, New York, (1988), 39, I l. lron and Steel Institute of Japan: Steel Handbook,Third Edition,

VolumeI, Maruzen, Tokyo, (1981), 19. M. Hino, S. Kitagawa and S. Ban-ya: Tetsu-to-Hanan~, 79
(1993), 34,

(Originally

published in Tetsu-to-Hagan~, 81 (1995),

I 17,

in Japanese)

C 1995 ISIJ

482 1