ISIJ International. Vol.

34
(1
994). No.
11
,
pp.
906-91
1
Mechanism
of
Steel Sheets
RedScale Defect Formation
in
Si-added Hot-rolled
Tomoki
FUKAGAWA.
Hikaru OKADA1)
and Yasuhiro MAEHARA2)
lron
and
Steel Research Laboratories,
SumitomoMetal Industries, Ltd..
Fuso-cho, Amagasaki, Hyogo-ken. 660 Japan.
1
)
Iron
andSteel ResearchLaboratories.
SumitomoMetal Industries, Ltd.,
Kashima-cho, Kashima-gun, Ibaragi-ken. 31
4
Japan.
2)
AdvancedTechnology Research Laboratories.
SumitomoMetal Industries, Ltd.,
Fuso-cho. Amagasaki. Hyogo-ken. 660
Ja
pan.
(Received
on
June
7.
l994; accepted
in final form
on
September
l6. 1994)
The
red scale,
which
is
one
of the major defects
on
hot-rolled Si
added steel sheets,
is
reproduced
6xperimentally.
On
the basis of detailed observation of the scale properties,
we
propose
the mechanism
of
formation of the red scale. Imcompletedescaling of
FeO
prior
to hot rolling
causes
red scale formation
even
in Si-free steels, since the reaction from FeOto Fe304and red Fe203
is largely accelerated by the breakage
of the FeO
scale, In
Si-added
steels, descaling
is quite difficult
to perform, becausethe eutectic
compound
of FeO/Fe.SiO*
is
formed at the scale/steel interface and penetrates
irregularly into both
upper
FeOand
lower steel sides. auite high strength of the eutectic
compound,
even
just
below the solidus
temperature
of
11
73'C,
can
also
make
it
difficult
to
descale.
KEYWORDS:
scale; descaling: Si-added
steelj red scale; hot rolling.
1. Introduction
Recently, for examplein the automobile industry, the
demand
for high strength steel sheets has increased for
the
purpose
of
energy
saving dueto the weight reduction.
Although
there
are
some
methods to strengthen the
materials,
among
them
solid solution hardening
is the
best
way,
becausethe other properties hardly be affected
by
this
method. For example, the precipitation harden-
ing affects significantly other properties such
as
forma-
bility
or
ductility.
The
ductility of hot rolled sheets
is
considerably reduced by the precipitation, since the
precipitates
act
as
initiation sites for ductile fracture.
In
case
of cold rolled sheets, since the formability
determined by
recrystallization behavior in the final
annealing will largely be affected by the precipitation,
drastic change
will
become
necessary
in order to keep
the original formability. Silicon is
a
reasonable alloying
element for the solid solution hardening
not
only from
the above-described view point but also
from the cost
performance aspect. In addition, the ductility is
not
largely affected by the small addition of
Si.
However,
on
the hot-rolled sheets of the Si-added
steel,
defects of heterogeneous red scale,
which reduce the
conunercial value,
are
often formed.1)
This
is
the
main
reason
why
the spread of this kind of steel sheet has been
limited. In addition, these defects
are
often inherited to
the cold rolled sheets, resulting in the plating defects in
the subsequent
process.
It is said that the red scale defect
on
the hot-rolled
sheets originates from the eutectic
compoundof
FeO/Fe2Si04with relatively
low solidus
temperature
of
l
173'C, which
is
generated in the furnace before hot
rolling.
The mechanismof the red scale formation,
however, has
not been
fully
undetstood
so
far.
Thus, the objective of this study
is
to
clarify the
mechanismof the red scale fornration in order to prevent
the scale defects in Si-added
steels.
2. Experimental Procedure
First,
we
investigated the actual state of the red scale
formed
on
the commercial hot strips of Si-added
steels.
Next,
we
tried
to reproduce the red scale
by the laboratory
hot
rolling.
Thechemical composition of the steels used
in the laboratory reproduction tests
is
given in Table
1.
Although there
is
a
significant difference of
Mn
content
between
Steels
I
and
2, it is well
known
that
Mn
does
Table
1. Chemical composition of the steel
used (massolo).
Steel
C
Si
Mn P S
Cu Ni Cr
Mo
A1
N
1
2
0.09
0.05
0.54
0.005
1
.46
0.15
0.009
0.009
0.0014
0.013
O
.O
l
0.01
0.02
0.02
o.02
o.02
0.01
0.01
0.019
0.024
0.0023
O.O016
C
1
994 ISIJ 906
ISIJ International. Vol.
34
(1
994), No.
11
Test A(Rol
I
ing without scale)
Weating the slab
(covered
with
)
SS sheet
Table 2.
Summary
of hot ductility and constituent ofscale
in Tests
A
and B.
Test B(Rol
I
ing with secondary scale)
Deformation of
FeO
Final constituent
Test Before rolling
by rolling of scale
Heating the slab
-
Scale forRlation
(covered ,vith
)
(exposed in air for 40s)
SS sheet
A
Thin scale Apparently ductile
FeO
+
Fe304
B
Thick scale Brittle fracture
FeO
+
Fe304
+
(Impressron
mto
steel)
ocFe203(red)
Test C(Rol
I
ing with primary scale
)
Heating the siab
-
r~~~~
r~~:~~1TT~~I
Descalln9
-
(without cover) Ll~li~Li
~
2-ndary scale formation
~rl~~:~~lTT~l
Desca
I[ng
(exposed in air for 40
s)
Fig. l. Block diagramofreproducing test ofscale before final
3-pass rolling.
The
slabs
were
heated at
1
220"C
for
2h
in
an
atmo-
sphere of 77.1"/oN2+ 14.30/0H20+8.201*C02with
or
without the stainless steel
cover.
After the Tests, the
slabs
were
cooled by water spray
in order to
suppress
the further changeof scale structure.
not
affect the red scale defect formation. In fact, the
red scale defects have
not
been reported in Si-free high-
Mn
hot-rolled steel sheets, in which considerable high
amount
of
Mnmore
than
I
wt"/* has been used for the
strengthening
purpose.
The30
mm
thick plates
cut from
continuously cast (CC) slabs
were
heated at
1
220'C for
2h
in
an
atmosphere of 77.10/0N2-14.30/0H208.60/0
C02, which simulated that of the actual combustion type
furnace, and hot rolled into
5
mm
thick hot bands by
3
passes.
Figure
I
showsschematically the three kinds of
tests employed
in this study. In Tests
A
and B, the slabs
were
covered with stainless steel sheets which prevented
the primary
scale
from forming in the furnace. In Test
A, the formation of the secondary scale
was
also
prevented by immediate hot rolling after
removing the
stainless steel sheet
cover.
Whereas,
in Test B, the slabs
were
exposedfor 40
s
in air after removing the
cover
in
order to form the secondary
scale. In Test C, the slabs
were
heated in the furnace without the
cover
to form the
primary
scale. After descaling, they
were
rolled
to 25
mm
by
I pass
and exposed for 40
s
in air for the secondary
scale formation. After being descaled again they
were
hot rolled
by
3passes
to bands with given thickness of
5
mm.
In
all the tests, after the final rolling the hot bands
were
cooled immediately by water
spray
in order to
suppress
further changeof scale structure.
On
these hot strips
and hot bands,
a
few
scale
properties
were
investigated by
means
of surface
roughness measurement,
optical microscopy, scanning
electron microscopy and
EPMA
analysis.
3.
Experimental Results
3.1.
Red
Scale
on
CommercialHot
Strips
Figure
2
shows
an appearance
of
a
red scale
on
the
commercial hot
strip,
which
was
hot-rolled from about
300
mm
thick
CC
slab to
6
mm
hot
strip.
Thechemical
907
composition
is
almost the
same
as
that of Steel
I
given
in Table
I.
Abnormal
red scale islands
are
elongated in
the rolling direction within the normal black scale matrix.
Figure
3
shows
a
surface roughness
profile in
a
transverse
direction after complete descaling.
Comparedwith the
relatively
smoothsurface after
removing the black scale,
the interface under the red scale
caves
irregularly in the
steel substrate.
3.2. Effect of SecondaryScale
on
the Final Structure
Here
the results of Tests
A
and
B
without primary
scale will be explained. In the Test
A
without the
secondary scale before rolling, the hot rolled hot bands
were
covered uniformly with black
~cale,
independent of
the kind of
steel.
Whereas, in Test
B
with the secondary
scale,
a
red scale
was
observed in both
steels.
X-ray
diffraction analysis revealed that the black scale
after Test
A
consisted of
FeOand Fe304,
as
shown
in
Fig. 4. After Test B, Fe203
was
also detected in addition
to FeOand Fe304.
It
should be noted that the
con-
stituents
were
independent of the kind of
steel.
Figure
5
shows
scale
structures
in the
transverse
cross
sections
of both
steels. After Test
A
without the secondary scale,
thin double layer
structure of FeO/Fe304
was
observed
to form
tightly in the both
Steels,
as
shown
in Figs. 5(a)
and
5(b). Whereas,after Test
B
with the secondary
scale,
the scale
structures
were very
complicated and
were
different from each other.
That
is,
in addition to
the
irregular double layer structure,
upper
layer of Fe304
was
broken by the rolling.
On
the broken Fe304
red
Fe203
Was
observed,
as
shown
in Figs. 5(c)
and
5(d).
The
results of Tests
A
and
Bcan
be summarized
as
Table
2. In Test A, the thin scale
can
bedeformedwithout
fracture during rolling,
and the scale constituent
is
preserved without
any
change. Whereas,
in
Test
B
with
the secondary
scale, the thick oxide layer
is
broken by
the shear deformation during rolling.
By
the increase of
surface
area
through the breakage supply of
oxygencan
be accelerated, Ieading to the formation of O-rich red
Fe203,
as
discussed later.
3.3. Effect of Primary Scale
on
the Final Scale Structure
Although
any
difference
between Steels
I
and
2
did
not
appear
in Tests
A
and B, marked
difference between
the both Steels
was
observed in Test
C
with the primary
scale,
as
shown
in Fig. 6.
The
colors of the hot bandsof
low
Si Steel
2
and high Si Steel
I were
black and
red,
respectively. Figure
7
showsback scattered electron and
SiK* X-ray image
on
transverse
cross
section of
Steel
1.
Zig-zag interface of steel/oxide
was
observed, and
oxide
particles
were
also formed
inside the steel,
as
shown
in
Fig. 7(a).
EPMA
analysis revealed that Si
atoms were
C
1994
ISIJ
ISIJ International, Vol.
34
(1
994), No.
11
2.
Appearanceofred scale defect in
a
Si-added hot rolled
steel sheet.
Thechemical composition
is
almost the
same
as
that
of Steel
I
shown
in Table
I.
R B R B R
45
.
OO
(
p
m)
O.
OO
45.
OO
o,
oo
7.
50 15,
Fig.
45 oo
Fig. 3.
O.
OO
7.
50
15.
OO
(
mm
)
Surface roughness profile after pickling in
a
transverse
direction of the sheet shown
in Fig. 2.
R: Red
scale
area
before pickling
B: Black scale
area
before pickling
(a)SteeJ
1
,
Test
A
(b)Steel
2
,
Test
A
FeO
a
Fe
FeO Fe304 a
Fe
Fe304
(c)Steel
1
,
Test
B (
d)
Stee
l 2
,
Test
B
a
Fe
FeO
a
Fe203
Fe304
a
Fe
FeO
Fe203
Fe304
47 48 50 52 54 48
26
(deg)
50 52 54
Fig. 4.
X-ray diffraction
patterns of the scales after Tests
A
and B.
(a) Steel l,
Test A; starting
temperature of rolling:
l I
18'C
(b) Steel 2,
Test A; starting
temperature of rolling:
I
122'C
(c) Steel l,
Test B; pre-oxidized from
1
184 to
I
OOO"C
for 30s before rolling
(d) Steel 2, Test B; pre-oxidized from
I
090 to 929'C
for 33
s
before rolling
Fe
1Opm
'
10
PrT,j~
~
f~TT~~i
~ 10Hm
Fig. 5.
Optical micrographs
on
transverse
cross
sections showing scale
struc-
tures.
(a) Steel
I
i
Test A; starting
tempera-
ture of rolling:
I I
18"C
(b) Steel 2,
Test A; starting
tempera-
ture of rolling:
I
122'C
(c) Steel
I
,
Test B; pre-oxidized from
1
184 to
I
OOO'Cfor 30s before
rolling
(d) Steel 2. Test B; pre-oxidized from
l
090 to 929'C for 33
s
before
rolling
Fig. 6.
Appearanceof the sheet after Test C.
(a) Steel
1
(b) Steel
2
C
1994 ISIJ
908
ISIJ International, Vol. 34 (1994). No. 11
20, p,=m,
Fig. 7. (a)
Backscattered electron and
(b) Si-Kc( X-ray image
in the vicinity of the primary scale/steel interface of
Steel
I
in Test C.
a
Fe
(1
10)
W
F
(200)
F
F
(231)
(112)(221)
W
=
FeO
w
F
=
Fe2S
i
0+
(111)
F F
F F
(1
31
X220)(031
)(
200)
55 50 45 40 35
2O
(deg)
Fig. 8.
X-ray diffraction pattern of Steel
I
in Test C, showing
the existence of
FeOandFe2Si04
in the primary
scale.
Back scattered electron image in the vicinity of the
primary scale/steel interface of Steel
2
in Test C.
Frg 10. Backscattered electron imageofremained
scale after
descaling the primary scale in Test C.
(a) Steel
I
(b) Steel
2
Fig. 9.
enriched in the oxide adjacent to the steel,
as
shown
in
Fig. 7(b).
Thecontent
ratio of Fe/Si in this region
was
2: I
in ato/o
.
Figure
8
shows
an
X-ray
diffraction
pattern
of the specimen shown
in Fig. 7(a) after
removing the
upper
oxide layers. Obviously diffraction peaks from
Fe2Si04
Were
detected,
as
indicated by mark
F.
From
these results, it
can
be
seen
that the oxide adjacent tQ
the steel is
a
eutectic product of FeO/Fe2Si04and the
upper
oxide
is
FeO. Figure
9
is
a
back
scattered. electron
image
on
the
transverse
cross
section of low
Si Steel
2
after Test C. The oxide layer consists of only FeO,
al-
though the interface of oxide/steel
was
complicated and
internal oxidation occurred samely
as
in high Si Steel
I.
Figure 10
illustrates
a
back scattered electron image
of the specimens after descaling the primary scale in
Test C, showing rema:ined scale
structure before hot
r.olling.
In high Si Steel
1,
a
large
amount
of oxide
re-
mains,
as shown
in Fig. lO(a).
The
eutectic
compound
of FeO/Fe2Si04
exists
between
steel
and FeO, and
is
penetrating irregularly into both
sides. In addition, the
eutectic
compound
entered into grain boundaries of the
upper
FeO. In
some
cases FeO
grains
are
enveloped by
the eutectic
compound. Such
very
complicated scale
909
Fig.
n.
Effect of rolhng temperature
on
the FeO/Fe2Si04
eutectic
structure of Steel
I
in Test C.
(a) Starting
temperature ofroning:
I
163"c
(b) Starting
temperature or
rolling:
I
ro7'C
structure
can
make
it difficult
to
descale.
On
the
contrary,
the primary scale in
low
Si Steel
2was
descaled
easily.
The
very
thin
FeO
film in Fig, lO(b)
seems
to be
formed by the oxidation after descaling.
Figure 11 showsthe effect of hot rolling
temperature
on
the scale
structure of high Si Steel
I
in Test C. In
this experiment, the primary scale
formed at
1
300'C
was
rolled directly without descaling at
different
tempera-
C
1994 ISIJ
ISIJ International, Vol.
tures
in order to
investigate the deformation behavior of
oxide layer during hot rolling.
When
hot rolling
tem-
perature
was
high enough, the oxide layer
was
deformed
plastically without
any
cracking,
as
shown
in Fig.
1
1(a).
In
case
of lower temperature
rolling, the eutectic
com-
pound of FeO/Fe2Si04remains with their
lammelar
structure, showing that these particles did
not deform
after the solidification. Instead,
FeO
surrounding the
eutectic
compounddeformed
largely, resulting in ductile
fracture,
as shown
in Fig.
1
1(b). This result
showsthat
the high
temperature
strength of FeO/Fe2Si04
is
much
higher than that of FeO.
4. Discussion
*
4.1.
Mechanismof
Red
Scale Formation
First
we
discuss
how
the red
Fe203forms through the
breakageof
an FeO
scale.
Figure 12 showsschematically
the
mechanismof red scale formation by fracture of
FeO
layer during rolling.
The kinds of oxides formed by
heating Fe
in air
are
FeO, Fe304and Fe203with the
volume
ratio of about 95
: 4:
l,
around
I
OOO'C.2)
That
is,
the scale consists mainly of
FeOunder normal
conditions without deformation. If the scale is
fractured
by hot rolling, the
area
of
FeO
particles exposedto
air
increases considerably.
To
these particles separated from
the
FeO
matrix, Iess
Featomsare
supplied.
Thus
oxygen
becomesoversupplied comparedwith the supplement of
Fe atoms from
steel, resulting in the
much
accelerated
reaction of FeO-Fe304-Fe203'This
final
product of
Fe203Iooks red. Asai et
al.3)
investigated the relationship
betweenthe color and
particle size of Fe203, andreported
that the depth of red color could be determined by the
fraction of fine
Fe203
particle~ of less
than
2
pm
in
diameter. Therefore,
it
can
beconcluded that the residual
scale before rolling
becomesthe
cause
of the, red scale.
In fact,
a
fractured scale
was
observed in the
part of the
red scale
on
the commercial hot rolled sheets.
4.2.
Mechanismof Red Scale Formation
in Si-added
Steel
In the
present experiment, the red scale
on
Si-added
steel
was
reproduced only by Test
C
wherethe primary
scale
was
formed
in the furnace and
was
not
reproduced
by Tests
A
and
B
without the primary scale. This result
showsthat the
cause
of the red scale defect
is closely
related
to the primary
scale.
The
cause
of
poor
descaling in Si-added steel has been
explained
so
far in
terms
of the fact that the impact by
high
pressure water
spray
is
reduced by the existence of
molten eutectic
compound
bctween
steel
and
scale.4)
According to Morita et
al.,5)
on
the contrary,
the
existence of FeO/FeS
eutectic
compound
with lower
melting point of 950'C, which
is
formed between
steel
and the FeO/Fe2Si04 compound
in high
S
steels,
accelerates descaling, in conflict with the previous
explanation. Okita et
al.6)
reported that the grain
boundary
eutectic
compoundmade
it difficult
to descale
by the anchor
effect,
bywhichthe scale is
firmly connected
with
steel.
Furthermore, Tuckand
Barlow7) pointed
out
that the depth of invasion of FeO/Fe2Si04
eutectic
C
1994
ISIJ 91
O
34
(1
994).
(a)
(b)
Fig.
1
800
l
600
1
400
1
200
Si
02
No.
11
a
Fe203
Fe304
Fe2~
_
FeO
g5:4:
I
(at 1000'C
)
~,.~~..
~
Fracture of FeOby rol
I
ing
OOO
~
~~
Powdered-aFe203(red)
Fe304
~.~.e_
~
PowderedFeO
~>
Fe304
~F
a
Fe2
3
(
red~
12. Mechanismof red scale formation by fracture of
FeO
layer during rolling.
(a) Scale structure before rolling
(b) Scale structure after rolling
2Liquids
Cr istbal
i
te +
Liquid
Fayal ite
+
Liquid
Tr
i
dyma
i
te +
Liquid
W~st
i e+
Li(
Tr
i
dym
i
te +
Faya
Ii
te Faya
Ii
te +
Wtist
i
tc
02 10 20 30 40 50 60 80 90 FeO
Fig. 13.
Fe2S
i
04
FeC~Si02phase
diagram.8)
Liquid
Wtist
i
te
compound
into
FeO
grain boundaries deteriorated
descalability
very
much.
Here
we
discuss the mechanismof penetration of
eutectic
compound
into
FeO
grain boundaries.
As
can
be
seen
from
a
FeO-Si02phase
diagram8) in Fig. 13, the
fraction of
FeO
is
much
larger than that of Fe2Si04
in
the
neighborhood of the scale/steel interface.
The state
of thermal equilibrium in this
system at oxidation
temperature of
1
220'C
is
"FeO(Wtistite)
+
Liquid". The
liquid phaseenclosing
FeO
grains becomesFeO/Fe2Si04
eutectic
compound
with the morphology
like "anchor"
after solidification.
In drder
to confirm the validity of such anchor
effect
on
the
poor
descaling ability, relation of descaling with
high
temperature
mechanical
property
of the Fe2Si04
should be also discussed in addition to
the morphology
effect.
That
is, if the eutectic
compoundhasgood
ductility
or
strength lowenough
for deformation, the anchor
effect
will be diminished. The
eutectic
compound
can
be
deformedwithout failure
by rolling
at
I
163'C
just below
the melting point (Fig.
I
l(a)).
In
case
of hot rolling at
l
107'C,
it
was
confirmed that the
compound
was
not
deformed and that
FeO
surrounding the compound
was
fractured (Fig,
I I
(b)),
showing that the compound
is
much
harder than FeO. This result does not
conflict
(a)
Fe203-->
Fe304-~~
FeO
FeO-Fe2S
i
04 l~
Fe
Fig. 14.
ISIJ International. Vol.
(b)
Desca
Iing
Rema
i
ned
34
(1
994). No.
11
FeO
FeO-Fe2S
i
04
(b)
Rol
Iing
Impression to steel and
fracture of remained FeO
~
Fe203( red)
Mechanismof red scale formation in Si
addedhot roned steet sheet.
(a) Formation ofthe primary scale (b)
Remainderofthe scale after descaling (c) Red-scale formation
with the
mechanismproposed by Okita et
al., in which not. Since the remained
FeO
scale partially
cut
into the
the
upper
FeO
scale is
strongly connected with
steel
by
steel is
fractured by rolling, the reaction,
FeO-~Fe304
H-
the
strong Fe2Si04 anchors. Fe203,
is largely accelerated by the oversupplement of
From
these results, the mechanismof red scale for-
oxygen.
Resultant fine particles
ofFe203Iooks thick red.
mation
in
Si-addei
steel
can
be depicted schematically (4)
Although the red scale
on
Si-added steels is
also
as
Fig. 14. In the furnace
a
thick scale consisting main- formed by the
same
mechanism
as
described above, the
ly of
FeO
is
formed prior to hot
rolling.
In addition, descaling ofthe primary scaleprior
to hot rolling
becomes
in
case
of Si-added
steel, the eutectic FeO/Fe2Si04 quite difficult
to achieve by the existence of irregularly
compoundformed
on
the FeO/steel interface
runs
shaped lamellar
compoundof FeO/Fe2Si04between
irregularly into both
FeOand
steel sides (Fig. 7).
When
steel
and
upper
FeO
scale.
descaling
is
carried
out at temperatures belowthe melting (5)
The
solidified
FeO/Fe2Si04eutectic
compound
point, since the strength of solidified eutectic
compound has
very
high strength
even
at high
temperatures 60'C
is
high,
it is difficult
to
remove
completely the
upper FeO below the melting point. Cutting into both
upper
FeO
scale
by the anchor
effect.
The remained
FeO
scale is
scale
and
steel sides accelerates the difficulty
of descal-
fractured easily
by the subsequent rolling,
and changed ing, Ieading to the red scale by the above-described
mto
Fe304and
finally into red Fe203 by the
reason
mechanism.
described before.
The molten eutectic FeO/Fe2Si04
compound
is
not
direct
cause
of the red scale defects.
REFE
R.E
NC
ES
l)
K. Onoda. H. Okabe, R. Nomiand N. Hase: SumitomoMet.,
5. Conclusions
20 (1968), 1.
2) S.
Mrowecand K. Przybylski: Oxid. Met.,
n
(1977), 383.
(1)
On
the Si-added hot-rolled steel sheets, scale
3) T. Asai,T. NakamuraandT. Inoue: CAMP-ISIJ,6(1993), 357.
defects consisting of stripe red andblack scales along the 4) S. Takizawa: Iron and steel
Handbook,
ed, by ISIJ, Maruzen,
rolling direction
are
often formed. Tokyo, 37.
(2)
Thered scale layer with
many
cracks
is
normally
5)
M. Morita, M, Nishida and T. Tanaka: Tetsu-to-Hagan~, 68
thicker than the black scale.
The
steel surface under the
(1982), S438.
red scale has
a concave,
because the
upper
surface
6)
M.Okita, A,Nagai,1. SinagawaandK. Horinouchi: CAMP-ISIJ,
2
(1989), 1509.
becomes
flat
by
rolling.
7) C.
W. Tuck and
J. Barlow:
hon
Steel, 45 (1972), 31.
(3)
Thered scale is
formed
easily
by remaining
FeO
8)
N. L.
Brownand
J. F, schairer:
Am.
J. Sci., 5th Ser., 24 (1932),
scale before hot rolling,
whether the steel contains Si
or
200.
91
1
C
1994
ISIJ