ISIJ International, Vol. 36 (1 996), Supplement, pp.

S77-S80

Calcium Treatment Technologies for Special Steel Bars and Wire

Rods

Yoshiaki KUSANO. MasamiWAJIMA.Ken SUGAWARA.1)

Yuji KAWAUCHI. HIDAI )
Masashi YOS
and Hiroaki HAYASH11)
Muroran R&D Laboratory. Nippon Steel Corporation. Nakamachi, Muroran. Hokkaido. 050 Japan.
)
1 Muroran Works. Nippon Steel Corporation. Nakamachi, Muroran. Hokkaido. 050 Japan.
(Received on May77. 1996, accepted in final form on November12. l996)

For the production by mediumsize bloom, sometrials were held, at first on the test bloom CC, next on
the proper CC, then the calcium treatment technologies for special steel bars and wire rods
wasestablished.
The appropriate calcium treatment condition for each steel grade shows various features, because the
equilibria of the alumina modification and the calcium sulfide formation by calcium addition are directly
affected by the contents of elements in the molten steel concerning these reactions. It
was found that
these features can be well explained by the thermodynamic data reported recently.

KEYWORDS:
calcium treatment; alumina modification; calcium sulfide formation; deoxidation equilibrium.

l .
Introduction 3.2. Experimental Results
Muroran No. 3CC, Iarge size bloom CC, was recon- (I) S45C: wasfound that to prevent nozzle clogging
It

Ca should be added to satisfy T.Ca/T.Al~~0.050.

structed to produce mediumsize bloom (162 The
mmx 162 detection rate of inclusions with the ultrasonic test (UST
mm)as well as large size, and have been producing
special steel since in June 1990. Before that, some Ca hereafter) decreases to very low extent whenthe chemical

treatment experiments were done with a test bloom CC composition of the heat satisfies T.Ca/T.AI 0.085.
(2) S25C: Tests were carried out by referring the
~
to examine the castability (to cast without nozzle clog-
ging) and the cast quality etc. Then the reconstructed S45C's results. Howeverin this case, the detection rate
of inclusions with USTkeeps very low when ratio
CCwas started up based on those test results. It was
found that the appropriate Ca treatment condition for
clogging.
~
T.Ca/T.AI 0.085. Besides, there was no sign of nozzle
each steel grade shows various features. Moreover the
performance shows differences between with the test 3.3. Discussion
bloom CCand with the proper CC. These features and (1) Ca-Modification Condition of Alumina Inclusions
differences were studied with thermodynamics focusing
Ca-modification reaction of alumina inclusions is
on the modification of alumina inclusions. studied with following equations.

2. Experimental Procedure Ca+0=CaO .......

..........(1)

2.1. Process 2Al+30=Al203 ....

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

l) Test process; BOF->transport-~Heat up by alu-

As for the apparent equilibrium constant,
minumoxidation-Slag reform->RH~,Ca-treatment~,
Test bloom CC [oloCa] ' [oloO]
= 2.50 x lO- 5 x ac*ol) -""'(3)
Proper process; BOFH,Slag reformH'RH-Ca-
2) [o/oAl]2 .
[o/oO]3 =3.47 x 10-11 x aAl20,2) .........(4)
treatment-~No. 3CC
were adopted. Eliminating [oloO] from Eqs. (3) and (4),
2.2. Steel Grades the following equation is obtained.
l) High-C Al-Si killed (S45C) 2) Low-CAl-Si killed
[o/oCa]3/[o/oAl]2
(S25C) 3) Low-CA1 killed (SWRCH) = 4.50 x l0-4 x a~*o/aAl'o, """'(5)

Table l. Chemical composition of steel. (mass"/*)

3. Ca Treatment for Al-Si Killed Steel with the Test
Bloom CC Grades C Si
S Al

3.1. Steel Grades I) S45S 0.45 0.20 0.020 0.0 15~0

High-C Al-Si killed (S45C) 2)
2) S25C 0.25 0.20 0.020 0.0 15~0
l)
Low-C Al-Si killed
3) SWRCH 0.08 0.03 0,020 0.015~O
(S25C) (Table l)

S77 O 1996 ISIJ

 ISIJ International, Vol. 36 (1 996). Supplement

(Nozzle clogging)
-E 60 OS-45C;good result in UST
~ e S-45C: bad tt
o
QL
c,)
u)
cls
50 C] S-25C:good
IS-25C; bad u
result in UST
~:~~S~) :~//~
~5~g:)

'
~
1::
0.8

0.6
'SWRCH I~olo
E 40 ~~~ O~\~~
> 0.4 O~ S45C
-H
O \~;Oe~~)'

\~~ ~~
l'
's2gc
e
o
~D O O ;~ _~
c: D~ZIC~t~!~--O~"~~ C~ 0.2
'~
~; 30 (,,
CTS -.--\,;;;'J'i _/' ~~-~~
o) Oo O o - - ---- -
Jb
co
0~Ti~4: e -0.2
c
(D
20
O 0.1 0.2 O3 O4 0.5 0.6

o O (StOpper erosion) Caconsumption (kg/t)

E 10
c: Fig. 3. Relations between castability and Ca consumption.
as

OoO iO 20 30 40
50 60
c
o
;:
Al in molten steel in TD( X I 0-3 masso/o)
cT~*_
I OO
~~
E 80 AI=0.025mass% SJ
Relations between USTresults ~
Q)

o~ s=0.020mass%
Fig. l.

T.Ca/T AI ratio,
of bar products and
c
o
U)co
60
T.0= 15mass m -CL
o
c:o~ 40
c!s
CaS ~
C CaO Multi-component cl)
:: 20 CaO u;
CD
A Al,O* (3,4'/.) Other composition ~c Al203 ID
•;~
S Si0= C-A-S (3,4'/.) O o
(6.9'/.)
O8 \~> NcaS(in inclusion)
1700 ~5
C-A ~l~ 0.6 .

\ NAl203(in oxide~
Js) I -
'~
(24.1'/.)
- zo 0.4
co
~
. -
-
1600
1500 o) a
~~71' c
C-A-CaS
oco

*~
(~ 0.2 m.p.
- ~-
- 1400 ~5 :;:

(62 2•/•) ~~:

~2z ^~ ~
o O IO 20 30 40
~ T. Ca (mass ppm)
( )meansthe number's ratio

Fig. 2. Composition of inclusions of S45Cbars of bad UST

Fig. 4. Influence of Caaddrtron on Inclusrons
result heats detected by UST.
'o(\~\ o~\~1 i\o(\~

eo
'~'$~\~$
\~ep ~~ep ~~ep
Substituting O.33 and 34 for a
c*o and aAl,o, Ofor the
'
60
cx~~e
o\e
\15L'~~o\e

properly modified Ca-aluminate,3) the bowshaped line (~'I; ~;~O:~S';

~)-
AI=0.025massa/a b~' J~)
in Fig. I
is obtained. Figure showsthe relation between I -E 50
S=0.020mass% ~r
,~!Cio'~~:c;fF
d~)'
~ir

chemical analysis of Ca and Al in molten steel and UST '~~ ~OiO

40 /.•"'
Optimumregion
results of bar products. Figure shows that nozzle did I ,,,
c,)
30 " o~G~~ ((\pt6100~)

J
cO
not clog when T.Ca/T.AI ratio was more than 0.085 E /..•
G(\i\cp:~\'~(\e ((1pc
which is the ratio modifying alumina inclusion properly. 20
/•"
l' ' . .
.

._mp~1750~C
(2) Difference between S45Cand S25Cin Modification
O
h: 10
/a."'
.
_.
. . .
- •

Behavior
O 40 50
Figure I also shows that S25Chas good USTresults o Io 20 30
(inclusion detection rate is low) with low T.Ca/T.AI ratio T. O (mass ppm)
and this area is wider than S45C's. Figure 2 shows the Flg' 5. Infiuence of total oxygen (T.o) on characteristics of
inclusions composition of S45Cbars which wasdetected indusions.

by USTand it
shows that there was muchCa-sulfide 4. Preliminary Experiments for Large Size Bloom with
in Ca-aluminate inclusions. Therefore for S45C, it is
considered that while the modification reaction occurs,
No. 3CC
the following reaction goes easily. 4.1. Steel Grades

Ca+S~>(CaS)........ ..........(6)
l) High-C Al-Si killed (S45C) 2) Low-CAl-Si killed
(S25C) 3) Low-CAl killed (SWRCH)
The reason why S45Cand S25Cshow such different
behaviors explained by the following
is effects.
4.2. Appropriate Ca-treatment Condition on Castability
Figure 3showsthe relations between Caconsumption
l) Interaction effect of for and C O Se~= + O.111,4) and the There is a clear difference between
castability.
eg= - 0.4214)
2) Effect of temperature difference at which Ca- A1-Si killed and Al killed steel. Thoughthere are
steel

injected the best castable points at low Caconsumption for Al-Si

according to their melting points
killed the more Ca addition increases,
steel, the more
nozzle clogging decreaces for A1 killed steel.
4.3. Discussion
Figures 4 and 5 showeffect of Caand oxygen content

O 1996 ISIJ s78

 ISIJ International, Vol. 36 (1 996), Supplement

on inclusion composition under the equilibria, using a composition can almost accurately be identified from
thermodynamic computation program for Ca-added T.Ca and T.O analysis of the molten steel.
Al-Si killed steel. Thermodynamicdata are based on the
data recommended by JSPS.4) These results show
(2) Ca Treatment Condition in Steel Composition
Investigating the relation between the ratio T.CalT.O
(1) Figure 4 shows that the more Ca is added the
of the molten steel and castability, the stopper erosion
more alumina is modified and melting point decrcases. increases as the ratio T.CalT.O rises. The appropriate
Whenthe melting point attain the minimumlevel the
T.CalT.O range not to occur nozzle clogging nor stopper
formation of CaSbegins wherc is the optimal Ca addi-
erosion O.4-0.6 which corresponds the appropriate
is
tion point. Then the more Ca is added
more than the inclusion composition CA-C3A5' Besides concerning
optimal point, the moreCaSis formed. CaSoccurs nozzle
about T.O, even if T.CalT.O is the samethe smaller the
clogging as well as alumina, so this explains the ex-
perimental results of Fig. 3for Al-Si killed steel.
T.O is, the lower the stopper erosion rate is. This
(2) Figure 5 shows that the iso-melting point lines means that it is efficient to decrease T.O to prevent
stopper erosion.
are drawn in the lower side of the lowest melting point
line, and the iso-CaS fraction lines
are drawn in the upper 5.3. Ca Treatment Conditions for High-C Al~Si Killed
side. The shaded region is the optimum Steel (S45C)
zone where the
quantity of Ca added is adequate to alumina inclusion (1) of SContent at Ca Addition on Inclusion
Effect
quantity. With this relation the behavior of low-C Al Composition
killed steel in Fig. 3 is reasonable because of its higher Figure 7 shows UST results of bar products by
total oxygen content than in Al-Si killed steel with changing S content before Ca treatment. This result
a
restriction of slag composition. shows that the inner defects of bars increases when S
goes over 0.020 "/.. CaSwas found at the site detected
5. CaTreatment Conditions for MediumSize Bloomwith ultra-sonic defect echo.
No. 3CC
(2) Ca Treatment Condition in Steel Composition
5.1. Steel Grades l) Low-C Al Killed (SWRCH)2) the relation between castability
Investigating and the
High-C Al-Si Killed (S45C) steel composition in the production line, Ca treatment
with good castability and without CaS formation is
5.2 Appropriate Ca Treatment Conditions for Low-C
Al Killed Steel (SWRCH)
0.6 ~~ T.CalT.O ~I .O which corresponds C12A7-CAin in-
clusion composition. Onthe other hand the appropriate
(1) and Inclusion Composition
Castability Ca treatment condition was studied by thermodynamic
Figure 6 shows the influence of inclusion composition calculation and CaSbegins to form at S 0.018 o/* with
Nozzle clogging occurs whenthe melt- =
upon castability, 0.7-1.0 in T.CalT.O ratio which almost corresponds to
ing point of inclusion is higher (higher A1203 side than
the operation results.
CA2 composition) than the casting temperature. Onthe
other hand, whenthe melting point of inclusion is lower 6. Dependenceof CaTreatment Condition on T.Ca/T.Al
than the casting temperature, stopper erosion occurs and on T.Ca/T.O
because the material of stopper is alumina graphite. As
As is mentioned above the appropriate Ca treatment
a result, it was found that the optimal inclusion form condition for HighLC Al-Si Killed Steel (S45C) was
will be between CAand C3A5' Moreover the inclusion
differently expressed in terms of steel composition as
follows.
2300 (1) T.Ca/T.AI should be morethan 0.085in this steel

~
with the bloom CC.
test
\ C]: Nozzle clogging
2100 \ e: Stable
(2) T.CalT.O should be 0.6~T.Ca/T.O~ 1.0 in the
\A: Stopper erosion operation results with No.3CC.
o \ /
\ dl
1900 \ 16
Q) \
:D \ 14
(:l \ ~l
/
\ 12
Q)CL
1700 \ l Dl
E \ 10
/
\ e I
H
(1) asting Temp
~
~ 8 /
/
1500 D
6 / D
o
Q) /
e) 4 /
1300 O 2
/
Cao
ao 20 40 60 80 AI203 D o O E llEr D
C3A CA2 o -
C12A7 CA CA6 0.008 O.
O12 0.01 6 0.020 0.024
Al203 (masso/o) [massoloS] before Ca treatment
Fig. 6. Infiuence of inclusions on castability for low-C Al Fig. 7. Effect of [mass"/*S] before Ca treatment on UST
Killed Steel (SWRCH). results of bars.

S79 O 1996 ISIJ

 ISIJ International. Vol. 36 (1 996). Supplement

Table 2. Comparison of T.Ca and T.O content of obtained. Therefore [Ca] should be supposed con-
good USTresult heats with Test CCand Proper siderably smaller than Ca,o. Figure 8 shows T.Ca and
CC(S45C). (mass"/*, * massppm) T.O content ranges of the heats with the test bloom CC
as well as with proper CC, comparing with an experi-
T.Ca* T.O* T.AI T.Ca/T.O (- ) T.Ca/T.AI (- ) mental slag-metal equilibrium data recently reported
Prop. CC 8I . I0.0 0.032 0.8 l 0.025 by Kimura.5) It is found that most of T.Ca (and most of
Test CC 21.2 21.9 0.020 0.97 O, 105
T.O) should be as oxide, especially for the data with the
test 8 shows T.Ca and T.O content
bloom CC. Figure
-2 ranges of the heats of this study, comparing with the ex-
bloom CC perimental slag-metal equilibrium data by Kimura.5)
production CC test
~ ~~/ (2) Consequently T.CalT.O can be an index for the

~
'~

U)
.3 Slag composition
(cao) :53.6mass%
(Si02)
\~i
DF modification degree of alumina inclusion, so the ap-
propriate Ca treatment condition can be expressed by
CQ :16 9mass% T.Ca/T.O.
(AI203):29.5mass%
E
LJ _4
(3) necessary that the relation
It is (Ca)ocCa,o
~: equilibrium
a) experiments should be in order that the appropriate Ca
satisfied
O DP: su persatu ration
treatment condition can be expressed by T.Ca/T.Al. This
experiments
proportion can vary largely according to the operation
.5 .4 -3 -2 condition, therefore it is difiicult that the appropriate
log (mass oloCa) Catreatment condition is expressed only by T.Ca/T.AI in
the long period operation.
Flg' 8. T.Ca and T Ocontent ranges ofthe heats ofthis study,
comparing with the experimental slag-metal equi-
hbrium data.6)
7. Conclusion

Calcium treatment technologies for special steel bars

To discuss massbalance of each element
this difference,
and wire rods, with various chemical composition, were
concerned with inclusion modification was studied sep-
arately by its form. Since Cais analyzed as total calcium
examined on sometypical steel grades.
only, then the following relation was supposed.
The appropriate Catreatment condition for each
(1)
steel grade shows featurcs respcctively, because the
T.Ca in molten steel = [Ca](dissolved Ca) equilibria of the alumina modification and the calcium
sulfide formation by Caaddition are directly affected by
+ Ca,o (Ca combinedwith O) thc contents of elements in molten steel concerning these
+ Ca,s (Ca combined with S) reactions.
As a was considered that the difference men-
result, it In particular,
(2) the different results concerning the
tioned above can occur by the following reasons. dependenceof the appropriate Ca treatment condition
(1) Comparingbetween Ca,o caluculated from T.O for high-C A1-Si killed steel (S45C)
upon the steel
of properly Ca treated steel and from the chemical composition were discussed slightly. Howevermuchmore
composition of inclusion properly modified with T.Ca investigation will be necessary, especially on the form-
analysis in the following manner, it was recognized that respective analysis of Ca.
most of the T.Ca should be Ca,o. Table 2 shows T.Ca
and T.O content of S45Cheats of which USTresults REFERENCES
were good, this meansinclusions were properly modified. l) Y. Miyashita and K. Nishika~a: Tetsu-to-Hagan~, 57 (1971),
Fromthese data, at first oxygen as oxide Ooxis calculat- 1969 .

ed by T.O-[O] O~., where [O] is caluculated from 2) T. Kawawa: The 19th Committee (Steelmaking), the Japan
= Soc. for the Promotion of Sci. (JSPS), Rep, No. 9927, (1976),
Al-deoxidation equilibrium T.AI analysis and aAl,o, for
2.
properly modified inclusion. Then Ca,o is estimated by 3) T. Fujisawa, M. Yamauchiand H. Sakao: CAMP-ISIJ, I (1988),
supposing Ca,olO~* ratio for properly modified inclusion lll5.
and Ca,s is negligible. Finally [Ca] is caluculated by 4) The 19th Committee (Steelmaking), the Japan Soc, for the

T.Ca-Ca,0=[Ca], then 3.7mass ppm for test CC's Promotion of Sci. (JSPS), Rep. No, 10588, (1984), 254.
5) T. Kimura and H. Suito: Metall. Trans. B, 25B (1994), Feb 33,
heats and 9.6mass proper CC's heats were
ppm for ,

o 1996 ISIJ S80