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Mechanism of Red Scale Defect Formation in Si-added Hot-rolled Steel

Sheets.

Article  in  ISIJ International · November 1994

DOI: 10.2355/isijinternational.34.906

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 ISIJ International. Vol. 34 (1 994). No. 11 pp.
,
906-91 1

Mechanismof Red Scale Defect Formation in Si-added Hot-rolled

Steel Sheets

and Yasuhiro MAEHARA2)

Hikaru OKADA1)
Tomoki FUKAGAWA.
lron and Steel Research Laboratories, SumitomoMetal Industries, Ltd.. Fuso-cho, Amagasaki, Hyogo-ken. 660 Japan.
1) Iron and Steel Research Laboratories. SumitomoMetal Industries, Ltd., Kashima-cho, Kashima-gun, Ibaragi-ken. 31 Japan. 4
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. Onthe basis of detailed observation of the scale properties, we propose the mechanismof
formation of the red scale. Imcomplete descaling of FeOprior to hot rolling causes red scale formation even
in Si-free steels, since the reaction from FeOto Fe304 and red Fe203 is largely accelerated by the breakage
of the FeOscale, In Si-added steels, descaling is quite difficult to perform, because the 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 makeit difficult to descale.
KEYWORDS:
scale; descaling: Si-added steelj red scale; hot rolling.

conunercial value, are often formed.1) This is the main

1. Introduction
reason whythe spread of this kind of steel sheet has been
Recently, for example in the automobile industry, the limited. In addition, these defects are often inherited to
demandfor high strength steel sheets has increased for the cold rolled sheets, resulting in the plating defects in
the purpose of energy saving due to the weight reduction. the subsequent process.
Although there are some methods to strengthen the It is said that the red scale defect
on the hot-rolled
materials, amongthem solid solution hardening is the sheets originates from the eutectic compound of
best way, because the other properties hardly be affected FeO/Fe2Si04with relatively low solidus temperature of
by this method. For example, the precipitation harden- l 173'C, which is generated in the furnace before hot
ing affects significantly other properties such as forma- rolling. The mechanismof the red scale formation,
bilityor ductility. The ductility of hot rolled sheets is however, has not been fully undetstood so far.
considerably reduced by the precipitation, since the Thus, the objective of this study is to clarify the
precipitates act as initiation sites for ductile fracture. mechanismof the red scale fornration in order to prevent
In case of cold rolled sheets, since the formability the scale defects in Si-added steels.
determined by recrystallization behavior in the final
annealing will largely be affected by the precipitation, 2. Experimental Procedure
drastic change will becomenecessary in order to keep
the original formability. Silicon is a reasonable alloying First,
we investigated the actual state of the red scale
element for the solid solution hardening not only from formed on the commercial hot strips of Si-added steels.
the above-described view point but also from the cost Next, we tried to reproduce the red scale by the laboratory
performance aspect. In addition, the ductility is not hot rolling. The chemical composition of the steels used
largely affected by the small addition of Si. in the laboratory reproduction tests is given in Table 1.
However, on the hot-rolled sheets of the Si-added steel, Although there is a significant difference of content Mn
defects of heterogeneous red scale, which reduce the between Steels I
and 2, it is well knownthat does Mn
Table 1. Chemical composition of the steel used (massolo).

Steel C Si
Mn P S Cu Ni Cr Mo A1 N
1 0.09 0.54 1.46 0.009 0.0014 O.O l 0.02 o.02 0.01 0.019 0.0023
2 0.05 0.005 0.15 0.009 0.013 0.01 0.02 o.02 0.01 0.024 O.O016

C 1994 ISIJ 906

 ISIJ International. Vol. 34 (1 994), No. 11
Test A(Rol I ing without scale) Table 2. Summaryof hot ductility and constituent ofscale

Weating the slab

in Tests A and B.
(covered with
SS sheet
) Test Before rolling
Deformation of
by rolling
FeO Final constituent
of scale

I
Test B(Rol ing with secondary scale) A Thin scale Apparently ductile FeO+ Fe304
B Thick scale Brittle fracture FeO+ Fe304+

)-
Heating the slab Scale forRlation (Impressron ocFe203 (red)
(covered ,vith (exposed in air for 40s) mto steel)
SS sheet

composition is almost the sameas that of Steel I given

in Table I Abnormal red scale islands are elongated in
I
Test C(Rol ing with primary scale ) .

the rolling direction within the normal black scale matrix.

r~~~~
- -
r~~:~~1TT~~I
Heating the siab Descalln9
(without cover) Ll~li~Li Figure 3shows a surface roughness profile in a transverse
direction complete descaling. Comparedwith the
after

Fig.
~
l.
2-ndary scale formation
(exposed in air for 40 s)

Block diagram ofreproducing

~rl~~:~~lTT~l

test
Desca ng I[

ofscale before final

relatively after removing the black scale,
smooth surface
the interface under the red scale caves irregularly
steel substrate.
in the

3-pass rolling.
The slabs were heated at 1220"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 change of 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 Mn I
more than wt"/* has been used for the
strengthening purpose. The 30 thick plates cut from
mm
continuously cast (CC) slabs were heated at 1220'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 thick hot bands by 3
mm
passes. Figure I shows schematically the three kinds of
tests employedin this study. In Tests
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 exposed for 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
by I pass and exposed for 40 s in air for the secondary
scale formation. After being descaled again they were
hot rolled by 3 passes to bands with given thickness of
5mm.In all the tests, after the final rolling the hot bands
were cooled immediately by water spray in order to
suppress further change of 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.
3.2. Effect of Secondary Scale on the Final Structure
Here the results of Tests and without primary A B
scale will be explained. In the Test without the A
secondary scale before rolling, the hot rolled hot bands
were covered uniformly with black ~cale, independent of
the kind of steel. Whereas, in Test Bwith 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 shownin
Fig. 4. After Test B, Fe203wasalso 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/Fe304was observed
to form tightly in the both Steels, as shownin Figs. 5(a)
A and B, the slabs B
and 5(b). Whereas, after Test 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 Wasobserved, as shownin Figs. 5(c) and 5(d).
The results of Tests A
and can be summarizedas B
Table In Test A,
2. the thin scale can be deformedwithout
fracture during rolling, and the scale constituent is
mm 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 oxygen can
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, markeddifference between
the both Steels was observed in Test Cwith the primary
scale, as shownin Fig. 6. The colors of the hot bands of

3. Experimental Results low Si Steel 2 and high Si Steel I were black and red,
respectively. Figure 7showsback scattered electron and
3.1. RedScale on CommercialHot Strips SiK* X-ray image on transverse cross section of Steel
2 shows an appearance of a red scale on the
Figure 1Zig-zag interface of steel/oxide wasobserved, and oxide
.

commercial hot strip, which was hot-rolled from about particles were also formed inside the steel, as shownin
300 thick CCslab to 6 hot strip. The chemical Fig. 7(a). EPMA analysis revealed that Si atoms were
mm mm
907 C 1994 ISIJ
 ISIJ International, Vol. 34 (1 994), No. 11
45 oo
OO .

(p m) R B R B R
O .
OO

45 OO .

OOO
o oo ., 7 50
. 15 OO
15,
(mm)
.

Fig. 2. Appearanceofred scale defect in a Si-added hot rolled Fig. 3. Surface roughness profile after pickling in a transverse
steel sheet. direction of the sheet shownin Fig. 2.
The chemical composition is almost the sameas that R: Red scale area before pickling
of Steel I shownin Table B: Black scale area before pickling
I .

(a)SteeJ 1 Test A
,
(b)Steel 2 Test A
,
Fig. 4.

FeO a Fe X-ray diffraction patterns of the scales after Tests A

FeO Fe304 a Fe Fe304 and B.
(a) Steel l, Test A; starting temperature of rolling:
l I 18'C
(c)Steel 1 Test B
, (d) Stee l 2 Test B
, (b) Steel 2, Test A; starting temperature of rolling:

a Fe I 122'C
FeOFe304 a Fe FeO
Fe304
(c) Steel l, Test B; pre-oxidized from 1184 to I OOO"C
a Fe203 Fe203 for 30s before rolling
(d) Steel 2, Test B; pre-oxidized from I 090 to 929'C
47 48 50 52 54 48 50 52 54 for 33 s before rolling
26 (deg)

Fe
Fig. 5.
Optical micrographs on transverse
cross sections showing scale struc-
'
10 PrT,j~ tures.
1Opm (a) Steel
i I
Test A; starting tempera-
ture of rolling: 18"C II
(b) Steel 2, Test A; starting tempera-
ture of rolling: 122'CI
(c) Steel
, I
Test B; pre-oxidized from
1 I
184 to OOO'Cfor 30s before
rolling
(d) Steel 2. Test B; pre-oxidized from
l 090 to 929'C for 33 s before
~
f~TT~~i
rolling
~ 10Hm

Fig. 6.

Appearanceof the sheet after Test C.

(a) Steel 1
(b) Steel 2

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 ISIJ International, Vol. 34 (1994). No. 11

20, p,=m,

Fig. 7. (a) Back scattered 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 W=FeO
(110)
w F=Fe2Si0+
(111)
W F
F (200)
F F F F F 200)
(231) (112)(221) (131 X220)(031 )(

Frg 10. Back scattered electron image ofremained scale after

55 50 45 40 35 descaling the primary scale in Test C.
2O(deg) (a) Steel I (b) Steel 2
Fig. 8. X-ray diffraction pattern of Steel I in Test C,showing
the existence of FeOand Fe2Si04 in the primary scale.

Fig. 9. Back scattered electron image in the vicinity of the

primary scale/steel interface of Steel 2in Test C.

enriched in the oxide adjacent to the steel, as shownin

Fig. 7(b). The content ratio of Fe/Si in this region
was
2I 8
: in ato/o Figure showsan X-ray diffraction pattern
.

of the specimen shownin 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
9
upper oxide is FeO. Figure 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-
Fig. n. Effect of rolhng temperature on the FeO/Fe2Si04
though the interface of oxide/steel was complicated and eutectic structure of Steel I in Test C.
internal oxidation occurred samely as in high Si Steel I .
(a) Starting temperature ofroning: I 163"c
Figure 10 illustrates a back scattered electron image (b) Starting temperature or rolling: I ro7'C
of the specimens after descaling the primary scale in
Test C, showing rema:ined scale structure before hot structure can make it difficult to descale. On the
r.olling. In high Si Steel 1, a large amount of oxide re- contrary, 2
the primary scale in low Si Steel was descaled
mains, as shownin Fig. lO(a). The eutectic compound easily. The very thin FeOfilm in Fig, lO(b) seemsto be
of FeO/Fe2Si04 exists between steel and FeO, and is formed by the oxidation after descaling.
penetrating irregularly into both sides. In addition, the Figure 11 shows the effect of hot rolling temperature
eutectic compoundentered into grain boundaries of the on the scale structure of high Si Steel I
in Test C. In

upper FeO. In somecases FeOgrains are enveloped by this experiment, the primary scale formed at 300'C was 1
the eutectic compound. Such very complicated scale rolled directly without descaling at different tempera-

909 C 1994 ISIJ

 ISIJ International, Vol. 34 (1 994). No. 11
tures in order to investigate the deformation behavior of Fe203
(a)
aFe304
oxide layer during hot rolling. Whenhot rolling tem-
perature was high enough, the oxide layer wasdeformed Fe2~
plastically without any cracking, as shownin Fig. 1(a). 1
FeO
_g5:4: I (at 1000'C )
In case of lower temperature rolling, the eutectic com-
pound of FeO/Fe2Si04 remains with lammelar
their
~,.~~..
~
structure, showing that these particles did not deform Fracture of FeO by rol I ing
after the solidification. Instead, FeO surrounding the
eutectic compound deformed largely, resulting in ductile OOO
fracture, as shownin Fig. 11(b). This result shows that
the high temperature strength of FeO/Fe2Si04is much
(b)
~
~~ Powdered-aFe203(red)
Fe304
higher than that of FeO.

4. Discussion *
~.~.e_
~
PowderedFeO~> Fe304 ~F red~3
a Fe2
4.1. Mechanismof RedScale Formation (
First wediscuss howthe red Fe203forms through the Fig. 12. Mechanismof red scale formation by fracture of FeO
breakage of an FeOscale. Figure 12 showsschematically layer during rolling.
the mechanismof red scale formation by fracture of FeO (a) Scale structure before rolling
(b) Scale structure after rolling
layer during rolling. The kinds of oxides formed by
heating Fe in air are FeO, Fe304 and Fe203 with the
volume ratio of about 95 : 4: l, around I OOO'C.2) That 1800
2Liquids
is, the scale consists mainly of FeO under normal
conditions without deformation. If the scale is fractured

by hot the area of FeOparticles exposed to air

rolling, l 600 Cr istbal ite + Liquid
increases considerably. To these particles separated from
the FeOmatrix, Iess Fe atoms are supplied. Thus oxygen
Fayal ite + Liquid
1400
becomesoversupplied comparedwith the supplement of
i
Tr dyma te + Liquid i
Fe atoms from steel, resulting in the muchaccelerated W~sti e+ Liquid
Li(
reaction of FeO-Fe304-Fe203'This final product of 1200
Fe203Iooks red. Asai et al.3) investigated the relationship i
Tr dymi te + FayaIi te FayaIite + Wtist itcte
betweenthe color and particle size of Fe203, and reported Si02 10 20 30 40 50 60 80 90 FeO
that the depth of red color could be determined by the i
Fe2S 04
fraction of fine Fe203 particle~ of less than in 2pm Fig. 13. FeC~Si02phase diagram.8)
diameter. Therefore, it can be concluded that the residual
scale before rolling becomesthe cause of the, red scale.
In fact, a fractured scale was observed in the part of the compoundinto FeO grain boundaries deteriorated
red scale on the commercial hot rolled sheets. descalability very much.
Here we discuss the mechanismof penetration of
4.2. Mechanismof Red Scale Formation in Si-added eutectic compoundinto FeOgrain boundaries. As can
Steel be seen from a FeO-Si02phase diagram8) in Fig. 13, the
In the present experiment, the red scale on Si-added fraction of FeOis muchlarger than that of Fe2Si04 in
steel
was reproduced only by Test where the primary C the neighborhood of the scale/steel interface. The state
scale wasformed in the furnace and wasnot reproduced of thermal equilibrium in this system at oxidation
A B
by Tests and without the primary scale. This result temperature of 1220'C is "FeO(Wtistite) + Liquid". The
shows that the cause of the red scale defect is closely liquid phase enclosing FeOgrains becomesFeO/Fe2Si04
related to the primary scale. eutectic compoundwith the morphology like "anchor"
The cause of poor descaling in Si-added steel has been after solidification.
explained so far in terms of the fact that the impact by In drder to confirm the validity of such anchor effect
high pressure water spray is reduced by the existence of on the poor descaling ability, relation of descaling with
molten eutectic compoundbctween steel and scale.4) high temperature mechanical property of the Fe2Si04
According to Morita et al.,5) on the contrary, the should be also discussed in addition to the morphology
existence of FeO/FeSeutectic compoundwith lower effect. That is, if the eutectic compoundhas goodductility
melting point of 950'C, which is formed between steel or strength low enoughfor deformation, the anchor effect
and the FeO/Fe2Si04 compoundin high S steels, will be diminished. The eutectic compoundcan be
accelerates descaling, in with the previous
conflict deformed without failure by rolling at 163'C just below I
explanation. Okita et al.6)
reported that the grain the melting point (Fig. I l(a)). In case of hot rolling at
boundary eutectic compoundmadeit difficult to descale l 107'C, it was confirmed that the compoundwas not
by the anchor effect, by which the scale is firmly connected deformed and that FeO surrounding the compound
with steel. Furthermore, Tuck and Barlow7) pointed out was fractured (Fig, II (b)), showing that the compound
that the depth of invasion of FeO/Fe2Si04 eutectic is muchharder than FeO. This result does not conflict

C 1994 ISIJ 91 O
 ISIJ International. Vol. 34 (1 994). No. 11
(a) (b) (b)
Impression to steel and
Fe203•--> fracture of remained FeO
FeO-Fe2Si04
Fe304-~~ Remained FeO ~
Fe203( red)
FeO
FeO-Fe2Si04 l~ DescaIi ng Rol Iing
Fe
Fig. 14. Mechanismof red scale formation in Si added hot 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 FeOscale partially cut into the
the upper FeOscale is strongly connected with steel by steel is fractured by rolling, the reaction, FeO-~Fe304H-
the strong Fe2Si04 anchors. Fe203, is largely accelerated by the oversupplement of
From these results, the mechanismof red scale for- oxygen. Resultant fine particles ofFe203 Iooks 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 samemechanismas described above, the
ly of FeOis 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/Fe2Si04 between
irregularly into both FeOand steel sides (Fig. 7). When steel and upper FeOscale.
descaling carried out at temperatures below the melting
is The solidified FeO/Fe2Si04eutectic compound
(5)
point, since the strength of solidified eutectic compound has very high strength even at high temperatures 60'C
is high, it is difficult to removecompletely the upper FeO below the melting point. Cutting into both upper FeO
scale by the anchor effect. The remained FeOscale 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 Fe304 and finally into red Fe203 by the reason mechanism.
described before. The molten eutectic FeO/Fe2Si04
compoundis not direct cause of the red scale defects. REFER.ENCES
l) K. Onoda. H. Okabe, R. Nomi and N. Hase: SumitomoMet.,
5. Conclusions 20 (1968), 1.

(1) On the
Si-added hot-rolled steel sheets, scale
2)
3)
S. Mrowecand K. Przybylski:
T. Asai,T. NakamuraandT.
Oxid. Met., n
(1977), 383.
Inoue: CAMP-ISIJ,6(1993), 357.
defects consisting of stripe red and black scales along the 4) S. Takizawa: Iron and steel Handbook, ed, by ISIJ, Maruzen,
rolling direction are often formed. Tokyo, 37.
(2) The red scale layer with manycracks is normally 5) M. Morita, M, Nishida and T. Tanaka: Tetsu-to-Hagan~, 68
(1982), S438.
thicker than the black scale. The steel surface under the
6) M.Okita, A,Nagai,1. Sinagawaand K. Horinouchi: CAMP-ISIJ,
red scale has a concave, because the upper surface
2(1989), 1509.
becomesflat by rolling. 7) C. W. Tuck and J. Barlow: hon Steel, 45 (1972), 31.
(3) The red 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
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