Materials Chemistry and Physics 148 (2014) 276e283

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Materials Chemistry and Physics

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Structural and spectroscopic characterisations of the surface oxide

scales and inclusions present on edge-burst hot-rolled steel coils
Anirban Chowdhury a, *, Ramasamy Iyyappan b, Dipanwita Majumdar c, Achintya Singha c
a

Research & Development, Tata Steel Limited, Jamshedpur 831001, India

Flat Product Technology Group, Tata Steel Limited, Jamshedpur 831001, India
c
Department of Physics, Bose Institute, 93/1, Acharya Prafulla Chandra Road, Kolkata 700 009, India
b

h i g h l i g h t s

First investigation and surface study report on edge-bursting issue of steel coils.

Detailed characterisations of the inclusions and surface oxide scales in steel.

Inuence of a particular type of calcium aluminate phase on process chemistry.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 16 February 2014
Received in revised form
20 June 2014
Accepted 24 July 2014
Available online 27 August 2014

Detailed structural and spectroscopic characterisations have been carried out on the inclusions and the
surface oxides present on edge-burst hot-rolled steel coils. Surface scales were characterised through Xray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy. Evidence of
different types of regular and non-stoichiometric Fe-oxides was found on the cracked surface of the steel
wire. Along with the surface scales inclusions with calcium aluminate and spinel was characterized using
Raman spectroscopy. The usefulness of Raman spectroscopy has been explored in detail for the characterisation of these inclusions; especially when XRD information ceases to be a limiting tool. The
samples collected from the clogged nozzle area were found to be of grossite (CaO$2Al2O3) phase and this
was also observed in the inclusions in the nished coils. It was found that this particular calcium
aluminate phase has a detrimental effect on casting and nal nished steel products.
2014 Elsevier B.V. All rights reserved.

Keywords:
Metals
Surfaces
Microstructure
Electron microscopy
X-ray diffraction
Raman spectroscopy and scattering

1. Introduction
The process of near net shape casting is an important method in
casting metal to a form close to that required for the nished
product. This is vital since it ensures that less machining is required
to nish the part. Several production processes have been developed for near net shape casting, most notably thin-slab casting and
strip-casting. Both thin-slab casting and strip-casting are forms of
continuous casting. Thin-slab technology provides two strategic
objectives: it allows steelmakers to increase the share of at
products efciently and economically and it also allows the substitution of high-strength microalloyed steel for commodity carbon

* Corresponding author. Materials Science & Engineering, Indian Institute of

Technology Patna, Patliputra Colony, Patna, BR 800013, India. Tel.: 91 612
2260232; fax: 91 612 2277383.
E-mail address: anirban.chowdhury@gmail.com (A. Chowdhury).
http://dx.doi.org/10.1016/j.matchemphys.2014.07.044
0254-0584/ 2014 Elsevier B.V. All rights reserved.

steel, thus contributing to weight reduction and decreasing the

demand for steel [1]. During continuous casting, slabs are heated in
a tunnel furnace from both sides. Edge burst defects have been
found on both of sides after rolling operations were carried out on
the slabs. In some cases, these defects may be restricted to the drive
or the operator side. The crack severity may be rated high if the full
coil is affected and respectively low or medium if few regions or if
half of the coil is affected. A representative gure depicting edgebursting is shown in Fig. 1. We have also found that these defects
mostly appear in the last heating sequence.
At the plant level, edge burst affected heats were collected for
three months. One common observation is that the aluminium
level is higher in these affected samples. In addition, there was
some problem in the casting area. The tundish region has been one
of the most important regions since all the major inclusions and
other oxidising elements in steel start to enter the system from this
region. In our case, there was a particular submerged entry nozzle
(SEN) which was getting clogged and hence it was chosen to be an

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277

standing of the interactions and inuence of residual and trace

elements [11e13].
The subject of defects in continuously cast products, during hot
rolling [14e16] and the effects of nozzle clogging [17,18] in defect
formation have been reported previously. In our case, the idea was
to investigate the issue from a chemical/structural point of view to
provide a scientic explanation for this continuing problem. Here
we present detailed characterisation of the inclusions present in
the nal steel body. It is important to note that the issue of edgebursting could be due to combinatorial reasons where the inuence
of simultaneous multiple factors could play a pivotal role leading to
the edge burst. However, we mostly conne ourselves to structural
and compositional investigations for this case study.
2. Experimental

Fig. 1. Representative image of the hot-rolled coils (as nished) illustrating edge-burst
defects.

important site for investigation as discussed in the following

sections.
This issue of surface edge-bursting is unique to thin-slab casting
and rolling and it is not restricted to any particular grade of steel. A
coil declared edge burst needs to be sent to the recoiler line to trim
the edge affected; each coil needs approximately two man-hours.
In addition to this, huge electrical energy is also consumed during trimming.
The casting disorder caused by nozzle clogging has been reported widely in the literature [2e5]. The main reason for clogging
is deposit formation developing from adhesion of solid inclusions
which may appear on parts of the casting equipment, for example,
in the ladle shroud/tundish nozzle, on the slide-gate, or in the SEN.
This phenomenon has epitomised a technical challenge for steelmakers since continuous casting was introduced. In the 1970s, the
calcium injection method was established and the effects of calcium in the steel melt were satisfactorily described. For casting
blooms or billets, another application of calcium treatment became
more vital, namely the conversion of solid Al2O3 inclusions to calcium aluminates [2,5]. Researchers have also suggested that addition of aluminium ensure the formation of a particular Caaluminate phase. Emphasis also has been placed on the need for
soft purging, which reduces the likelihood of clogging in the caster.
Inclusions in steel, typically comprising alumina, spinel, sulphide, oxisulphide, carbonitrides etc, are fairly common and have
been widely studied [6e8]. Alumina inclusions normally occur as
deoxidation products in the nal nished steel-grade products.
Pure alumina has a melting point of 2054  C [9], i.e., the solid-state
alumina inclusions will generally be present in the liquid steel.
Alumina inclusions are particularly harmful because they tend to
clog the refractory nozzles. One way to circumvent this problem is
injecting calcium in to the ladle before transferring the steel to the
tundish. The calcium reacts with the alumina inclusions to form
aluminates (CaO$Al2O3) that have a much lower melting
temperature.
Another known effect of calcium injection is that it globularizes manganese sulphide (MnS) inclusions. The formation of
Ca-aluminate has one more drawback: it has been reported that
the aluminates, having a higher melting point than the sulphide
inclusions, solidify rst and start to act as the nucleation sites for
the solidication of the (Mn,Ca)S inclusions [10]. The problems
of hot shortness and high temperature embrittlement have also
been a major concern for a surprisingly long time and researchers have placed emphasis on the need for an under

The grade of steel in consideration had a nominal composition

of 0.01e0.1% C, 0.15e0.3 Mn%, 0.04% S, 0.04% P, 0.15% Si, 0.02e0.07%
Al, 0.002e0.004% Ca, 0.0059% N, with the rest Fe (in wt%).
The analysis of the phase aggregate was carried out through Xray diffraction (XRD) with a Panalytical X'pert PRO XRD unit using
CuKa radiation (0.154 nm). The diffractometer was operated at a
voltage of 45 kV and current of 40 mA.
For scanning electron microscopy (SEM) studies, the hot-rolled
coil samples were cut and hot mounted with suitable resin for
mechanical grinding and polishing with up to 0.1 mm diamond
paste and etching with Nital (2 vol% nitric acid in ethanol). The
microstructure and surface morphology of the samples were
observed by a scanning electron microscope (SEM, SUPRA 25, ZEISS
FEG) equipped with an energy-dispersive spectrometer (EDS). The
energy used for analysis was 15 kV.
The Raman scattering experiments were performed using a
micro-Raman setup consisting of a spectrometer (model Lab RAM
HR, JobinYvon) and a Peltier-cooled charge-coupled device (CCD)
detector. An air cooled argon ion (Ar) laser having wavelength of
488 nm was used as the excitation source and was focused by a 10
microscope objective to a spot of about 10 mm diameter. The samples were analyzed in the 180 backscattering conguration with
600 grooves/mm grating. All Raman spectra were recorded at room
temperature.
3. Results
3.1. XRD
As a preliminary analysis of these edge burst coils, XRDs were
carried out on the surface of the crack and the region without any
cracks to look for any noteworthy differences. It was found that
both the samples almost have the same sets of peaks with minor
alterations of intensities, Fig. 2. Fe3O4 (JCPDS le no. 19-0629), was
found to be the predominant oxide existing in both the samples. It
is important to note that cubic g-Fe2O3 (JCPDS le no. 39-1346) has
similar peak positions with small positive shifts. The 100% intensity
peak appears at 35.63  2q, but, after analysing all the peak positions, we decided to index the major phase as Fe3O4 due to the
proximity of the peak positions and the reasonable matching of
their intensity ratios as reported for JCPDS le no. 19-0629.
The second oxide was of Fe2O3 (JCPDS le no. 33-664); the
proportion of the phase was signicantly low compared to Fe3O4.
Very small intensity new peaks were noted at 38.66 and 65.08  2q
for the crack surface of the steel coil but their intensities were too
low to correlate them to any new phase/compounds.
As a next step of investigation, the broken edge surface was
machined and ground and the collected particles were submitted

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A. Chowdhury et al. / Materials Chemistry and Physics 148 (2014) 276e283

Fig. 2. XRD patterns on the surface of the edge crack and region without any crack;
peak proles conrm the presence of Fe3O4 and Fe2O3.
Fig. 3. XRD pattern of the sample collected from the tundish preparation area.

for XRD. The XRD pattern showed mostly -Fe (JCPDS le no. 06696) peaks arising from the steel matrix.
The SEN that was being clogged was broken to collect the
sample for analysis. We had a preliminary idea about the nonmetallic inclusions in steels (mainly oxides of Ca, Al, Mg etc and
sulphides) and wanted to investigate which particular component
was responsible for the clogging. Also, from microstructural analyses, it was evident that calcium, aluminium and magnesium
(trace) were present in the edge-broken samples e we therefore
decided to trace their source of entry. The sample from the tundish
preparation area was collected and pulverized at the Coal Characterization Laboratory and was sent for XRD analysis.
The XRD pattern, as shown in Fig. 3, matches predominantly
with grossite (CaO$2Al2O3, CA2) (JCPDS le no. 23-1037 and 461475) and minor amounts of Fe3O4 (JCPDS le no. 26-1136) and
MgAl2O4 (JCPDS le no. 21-1152). The sample matches very well
with both the standard patterns of grossite (CA2) (JCPDS le no. 231037 and 46-1475).
The only signicant change in the intensity pattern ratios is for
the peaks at 36.88, 59.35 and 65.23 2q and it can be explained by
the presence of MgAl2O4 (JCPDS le no. 21-1152) and Fe3O4 (JCPDS
le no. 26-1136) which have their 100% intensity peaks at 36.85 and
36.82 2q respectively. It is therefore inferred that the contributions
to the peak intensity in our sample for the peaks mentioned above
are mainly due to Fe3O4 and MgAl2O4 together with the CA2 phase.
The peaks of individual phases have been marked and are listed in
Table 1, and the sample data, along with a stick pattern of the
reference les are shown in Table 1. For ease of understanding, we
have arranged the data according to their intensity ratios. We

decided not to mark the peaks in our data le since not only the
individual peaks but peaks (major and minor) along with their
intensity ratios complete the true representation of any phase. The
stick pattern in Fig. 3 will help in giving a clearer picture on phase
identications. We have searched for sulphide compounds but
could not nd any signicant evidence for these.
It is useful to mention that some evidence for other related
phases has been noted, but the peak matching (2q and d-spacing)
was found only with their 100% intensity peak in most cases.
Moreover, their actual intensities in the sample were not very high
and hence they were not included in the Table for discussion. These
phases are Fe3O4 (JCPDS le no. 19-0629), rhombohedral aFe2O3(JCPDS le no. 33-664) and calcium iron oxide, Ca4Fe14O25,
(JCPDS le no. 13-342).
We have also observed evidence of Fe3O4, with matches between two different existing standard JCPDS patterns of Fe3O4. For
the cracked surface region, the Fe3O4 pattern matches le no. 190629, whereas, for the sample collected from tundish preparation
area, it matches closely with le no. 26-1136. Both the standard les
depict the same space group (Fd-3m) and group number (227) for
Fe3O4, although their peak positions are different.
In JCPDS le no. 26-1136, Fe3O4 has been identied as a
magnetite sample at very high pressure and it displays a lower
lattice parameter (8.09 ) compared to the Fe3O4 in JCPDS le no.
19-0629 (8.396 ). Although evidence of both these co-existing
structures has recently been reported by other researchers [19], it
is not fully understood why they would appear in our samples. A
possible reason may be hypothesized based on the structure of

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279

Table 1
Detailed peak list match for the sample collected from tundish with reference to standard JCPDS patterns.
Sample data collected from Tundish


2q

25.480
34.578
36.875
20.039
29.018
32.586
31.105
65.234
33.093
44.886
24.748
59.353
35.481
19.046
44.119
51.922
60.174
50.715
45.390
68.290
46.912
36.281
27.666
61.181
48.743
70.568
41.462
38.811
48.051
56.669
54.400

CA2 (CaO$2Al2O3) (JCPDS le no. 23-1037)

d []

I [%]

3.4930
2.5919
2.4356
4.4275
3.0747
2.7457
2.8730
1.4291
2.7048
2.0177
3.5947
1.5558
2.5280
4.6560
2.0510
1.7596
1.5366
1.7987
1.9965
1.3724
1.9352
2.4741
3.2218
1.5137
1.8667
1.3336
2.1761
2.3185
1.8920
1.6230
1.6852

100
62.22
58.52
48.78
34.36
32.6
29.29
24.85
24.22
23.4
22.39
21.06
17.78
14.86
12.59
11.84
11.49
9.44
8.86
8.15
7.33
7.14
6.4
6.01
5.91
5.87
5.82
5.79
5.62
5.27
5.03

2q

d []

I [%]

25.428
34.481
36.868
19.982
28.967
32.497
31.005
65.186
33.002

3.5000
2.5990
2.4360
4.4400
3.0800
2.7530
2.8820
1.4300
2.7120

100
60
16
55
30
25
20
2
25

24.710
59.304
35.394

3.6000
1.5570
2.5340

20
4
15

44.052
51.847
60.198
50.644
45.306
68.311
46.840

2.0540
1.7620
1.5360
1.8010
2.0000
1.3720
1.9380

16
10
12
10
6
10
6

27.594
61.166

3.2300
1.5140

6
4

70.480
41.365

1.3350
2.1810

6
6

56.631
54.302

1.6240
1.6880

6
6

Fe3O4 and the degree of undercooling that it undergoes during its

formation. This undercooling eventually dictates nature and
amount of stress in the parent lattice.
However, there is link between these two JCPDS patterns; one
pattern can be explained as a derivative of the other given the
condition that their respective d-spacings go through a lateral shift
of approximately 4%. The lattice parameter is similarly slightly
greater (~4%) for 19-629 and the density values follow a similar
trend. This also suggests that the Fe3O4 (JCPDS le no. 26-1136)
holds a more compact structure and the slightly relaxed bonding in
Fe3O4 (JCPDS le no. 19-629) can be explained in terms of increased
vacancy/defect concentrations within the lattice. Fe3O4 has an inverse spinel structure which consists of a cubic close packed array
of oxide ions where all the Fe2 ions occupy half of the octahedral
sites and the Fe3 ions are split evenly across the remaining octahedral and tetrahedral sites [20].
3.2. SEM-EDS
The cracked surface of the edge burst coil was investigated
under SEM. Two distinctly different microstructures with different
Fe/O atomic ratios were found (based on selected area EDS),
Figs. 4e5. One has a round and globular morphology (Fig. 4) while
the other depicts a aky and acicular microstructure (Fig. 5).
Different locations were investigated from various portions of
numerous edge burst samples and it was found that, the globular
morphology of Fe-oxide occurs in abundance throughout the
sample. There are sufcient reports connoting the presence of
various non-stoichiometric defect oxides with different valence
states of iron [21,22]. We have also noticed that the XRDs of crack
oxide (Fig. 2) predominantly match with Fe2O3 and a minor amount

Fe3O4 (JCPDS le no. 26-1136)



2q

MgAl2O4 (JCPDS le no. 21-1152)

d []

I [%]

36.821

2.4390

100

65.186

1.4300

50

59.304

1.5570

40

2q

d []

I [%]

36.853

2.4370

100

65.243

1.4289

55

44.833

2.0200

65

59.371

1.5554

45

19.029

4.6600

35

of Fe3O4. The phase diagram for the ironeoxygen system indicates

that FeO is not stable below 570  C, and that the oxide that can
coexist with iron is Fe3O4. It is also thermodynamically favoured for
Fe2O3 to form on Fe3O4 [23]. Consequently, considering the margin
of error of the EDS analyses, the two different oxide microstructures
could be close to either Fe2O3 and/or Fe3O4.
The SEM investigation of the exposed crack surfaces did not
reveal anything signicant other than different proportions of iron
oxides. We decided to move away from the main visible area of the
wide crack and to investigate the trajectory of the crack line by SEM.
An edge of an edge burst coil where the crack can be seen by naked
eye was selected for this purpose. The sample was machined, polished and mounted. EDS analyses showed evidence of oxides
involving calcium, aluminium and iron (points 1 and 2 in Fig. 6);
points 3 and 4 depict the presence of iron oxide only. A similar
trend repeated for a spherical inclusion, as seen in point 1, Fig. 7,
although EDS data along the ne crack line again conrm the
presence of Fe-oxide (point 2, Fig. 7). In all cases, the cavities were
found to be transgranular, and the inclusions here may be related to
phases involving calcium aluminate. It may not be straightforward
to correlate the presence of near-spherical inclusions with the
initiation of the crack line but the reason can be hypothesised as
follows:
The intrusion cavities are found to be 1e1.5 mm in size and may
be smaller in some regions. These Ca-aluminate transgranular
cavities start growing due to an imbalance in the Ca and Al compositions during the forming and cooling of the steel sheet. They
then combine to form a chain (i.e., hair-like thin crack) and propagate extensively, nally leading to an edge burst. We do not see
much evidence of Ca-aluminate in the open crack regions; probably
they are being covered by thick Fe-oxide. In other sections of these

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A. Chowdhury et al. / Materials Chemistry and Physics 148 (2014) 276e283

Fig. 4. SEM micrograph with EDS data (for point 3) for point analyses for the iron oxide with globular morphology.

Fig. 5. SEM micrograph with EDS plot for area analyses for the iron oxide with acicular morphology.

coil samples, evidence for sulphide and spinel (probably MgeAl

spinel) inclusions were also found, Fig. 8.
We have also checked for the evidence of Cu and Sn as they are
frequently found responsible for the problems related to hot

shortness [12,13] but from XRD and SEM analyses, we could not nd
any signicant presence of them in our samples. However, at this
stage it will be very difcult to rule out the possibility of hot shortness due to residuals in steel which may nally lead to edge cracking.

Fig. 6. SEM-EDS analyses (for point 2) of the mounted and polished coil sample for the inclusions involving calcium aluminate.

A. Chowdhury et al. / Materials Chemistry and Physics 148 (2014) 276e283

281

Fig. 7. SEM and EDS analyses (for point 1) of the mounted and polished coil sample showing the evidence of a spherical inclusion involving calcium aluminate.

3.3. Raman spectroscopy

For further conrmation of the presence of these inclusions and
other relevant phases on the steel surface, we have carried out a
Raman spectroscopic examination as this is one of the most
essential non-destructive spectroscopic methods. Raman spectroscopy is an analytical technique that gives information about
molecular bonding, crystalline phase, orientation and symmetry in
the case of a single crystal sample [24]. In most cases, XRD and SEM
studies have been used to characterise the non-metallic micro-inclusions in steel [6]. In this study, the advantage of Raman spectroscopy has been demonstrated for the investigation of the edgebursting phenomenon.
The measurements were performed at low laser power to avoid
the effect of laser heating. Fig. 9 shows the Raman spectrum of the
sample collected from the tundish preparation area; XRD of the
same is shown in Fig. 3. The observed Raman bands and the corresponding literature data are listed in second and fth columns of
Table 2, respectively. The strong band at 409 cm1 is due to symmetric bending of the AlO4 in Grossite [25]. We have also observed
some moderately intense Grossite related peaks. Apart from the
modes of Grossite, the spectrum shows the presence of iron oxide,
which is expected in our sample. The modes at 306, 540 and
610 cm1 are due to Fe3O4 [26,27]. The strong peak observed at
354 cm1 is related to g-Fe2O3 [26]. Other week bands at 202, 340,

362 and 436 cm1 may be due to the presence of a trace amount of
MgAl2O4 [28]. It is very difcult to distinguish between Fe3O4 and
MgAl2O4 based on their XRD peak positions. However, their Raman
bands are entirely different and can therefore be used as a tool to
distinguish between surface scale (Fe3O4) and inclusion (MgAl2O4)
as shown in Table 2. Discrepancies between the observed and reported modes related to peak position, intensity and spectral
feature may be due to the differences in crystallite size and defect
or impurity induced lattice modications arising from different
process chemistry variations.
Fig. 10 shows the Raman spectra of polished and mounted samples (SEM is shown in Fig. 6) involving the edge of a coil and
depicting a severe edge-bursting (black curve) moreover, in some
regions, a coil section with the edge chipped off (red curve). The
peaks are listed in Table 2. The Raman spectra of these samples
conrm the presence of CaO$2Al2O3 (CA2), Fe3O4, g-Fe2O3 and
MgAl2O4. The vibrational modes of CA2 are distributed in the frequency range from 200 to 900 cm1. The bands above 650 cm1
might be associated with tetrahedral aluminate stretching motions
[29]. In both samples, several modes originate from the MgAl2O4. An
intense peak around 707 cm1 could be assigned to the stretching
mode of AlO6 polyhedra, which are substructures in calcium ferritetype MgAl2O4 [28]. This result implies that the percentage of spinel
inclusions (MgAl2O4) is also signicant in the nished steel samples,
although they may not be responsible for edge cracking.

Fig. 8. SEM-EDS analyses (for point 2) of the mounted and polished coil sample depicting the presence of sulphide inclusions.

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A. Chowdhury et al. / Materials Chemistry and Physics 148 (2014) 276e283

Fig. 9. Raman spectrum of the sample collected from the tundish preparation area.

Fig. 10. Raman spectra of polished and mounted sample (SEM shown in Fig. 6) involving
the edge of an edge burst coil (black curve at the bottom) and a coil section with an edge
chipped off in some regions (red curve at the top). (For interpretation of the references to
colour in this gure legend, the reader is referred to the web version of this article.)

Table 2
Observed Raman peaks of selected samples as discussed in XRD and SEM analyses; reported modes are listed in last column.
Compound

Observed Raman mode (cm1)

Observed Raman mode (cm1)

Observed Raman mode (cm1)

Sample detail

Black powder collected

from the tundish area

Polished and mounted sample

involving edge of an burst coil

Coil section with edge

chipped off at some regions

e
250
e
321
409
457
568
e
686
e
e
e
e

222
250
279
321
415
455
570
661
e
714
756
806
853

222
e
287
317
408
e
568
664
e
714
756
806
853

Source Ref. [29]

222
253
283
321
412
457
568
660
686
714
756
806
852

306
540
610
e

312
538
610
669

300
535
610
e

306
538
616
668

354
e
e

354
507
700

e
507
700

Source Ref. [26]

350
500
700

e
e
202
e
340
362
e
e
e
436
e
e
e
e
e
e
e
e
e
e

e
e
e
237
340
e
381
e
416
e
e
486
e
486
e
574
594
638
708
744

173
192
202
237
340
362
379
408
e
436
470
486
568
486
568
e
e
637
707
e

Source Ref. [28]

173
192
202
237
340
362
381
408
416
436
470
486
567
486
567
574
594
638
708
744

Grossite
CaO$2Al2O3 (CA2)

Fe3O4

g-Fe2O3

MgAl2O4

Reported Raman
mode (cm1)

[26]
[26]
[27]
[26]

A. Chowdhury et al. / Materials Chemistry and Physics 148 (2014) 276e283

4. Discussion
The addition of calcium to steel which contains alumina inclusions causes the compositions of these inclusions to change from
pure alumina to a CaOeAl2O3 binary system in which the melting
point of the calcium aluminates will fall as CaO content increases
until a liquid oxide phase occurs at approximately 22% CaO. The
liquid phase content continues to increase as CaO content rises
further until the liquid phase is 100% at 35% CaO composition. The
minimum melting temperature for the liquid calcium aluminate is
at around 1400  C, i.e., such liquid calcium aluminates may be
present in liquid form until, or even after, the steel solidies.
Assessments of the CaOeAl2O3 system have been made by
various research groups but a disagreement has focused around
stability issues regarding CA2 [30]. Based on theoretical calculations, it has been reported that the CA2 compositions are not stable
at very low temperatures. The melting point of CA2 is around
1720e1770  C but the eutectic compositions involving CA2 tend to
separate at around 1600  C, which is very close to the actual temperature during casting. This liquid slag solidies as calcium
aluminate (CA2) at 1470  C. Sulphide precipitation proceeds further
as well. With decreasing temperature, solidication continues and
ends at about 1440  C. At the same time, the oxide inclusions
change their compositions from CA2 to CaO.6Al2O3 and nally to
Al2O3 [5].
Since the initial liquid contents develop as soon as the CaO.Al2O3
compound is formed, it signies that calcium to a total oxygen ratio
of 0.4 is necessary for such inclusions. At this ratio and above,
partial or complete liquid calcium aluminates occur.
The conversion of alumina to calcium aluminates occurs
initially, until all the inclusions, i.e., oxides, in steel are present only
in liquid form. The formation of solid calcium sulphide then occurs
when an addition of calcium is increased further to a higher level.
The range in which all the oxides have been liqueed and no solid
sulphides have yet formed is regarded as the optimal window for
calcium treatment.
The effect of inclusions on the castability of steel has been reported previously [2]. Steel containing inclusions of pure alumina
has only a moderate castability but this castability deteriorates
drastically with the formation of calcium aluminate inclusions. It
has been reported that the castability of steel is worst for any
composition with calcium to total oxygen ratio of 0.4 (approx.). This
indicates that the CaO$2Al2O3 (CA2) is the most deleterious phase
responsible for the degradation of steel castability. However, the
castability improves signicantly with the emergence of phases
with higher calcium to total oxygen ratio, e.g., CA, C12A7 etc. [2].
We have found enough evidence of surface scales and have
characterised them suitably. However, it is to be noted that surface
oxidation by scale formation in steel coils is a generic and unavoidable phenomenon. The exact causes of edge-bursting are
unknown and will need a greater in-depth study combining all the
process chemistry parameters. The role of one particular type of
calcium aluminate phase may be correlated to surface cracking of
steel coils in this regard. The two ends of the slabs from which coils
are rolled are continuously heated by burners at both ends. This
heat generates huge thermal stress between already existing submicron sized calcium aluminate inclusions and the steel matrix.
Literature reports suggest that the thermal expansion coefcient is
around four times larger for steel compared to pure CA2 type
phases [31,32]. Therefore, the differential thermal stress proles
owing to their signicant difference in their respective expansion
coefcient could easily result in the nucleation of cracks. Concentration of such localised inclusions would amplify this stress effect
and would result in the formation of a crack as a measure of stress
relaxation. These edge-bursting defects are mostly observed in the

283

last sequence of the heat. The logical explanation for this could be
related to the density of the inclusions with respect to the liquid
metal. Owing to their higher density, it is expected that the CA2 and
related inclusions will settle down at the bottom and would mix
mostly when the last slab is cast. However, as mentioned earlier, we
would like to emphasise that the genesis of the edge burst problem
may not just be correlated with a single cause but could be due to a
number of microstructural, chemical and/or thermodynamic process alterations.
5. Conclusion
The results involving structural, microscopic and spectroscopic
characterisations on the edge-burst steel coils reveal the presence
of calcium aluminate (CA2) inclusions along with some other
sulphide and spinel inclusions. The samples collected from the
tundish area mainly showed the presence of CA2 phase. The
presence of high CA2 phase inclusions is unacceptable for castability should be carefully controlled during processing. The formation mechanism of these CA2 inclusions needs to be
investigated in detail in relation to the process chemistry and kinetics. This work also shows the Raman spectroscopy as a nondestructive technique for the study of inclusions in steel. The
combination of other factors such as thermal history, process
chemistry, etc. needs to be investigated in order to get a thorough
explanation of the edge-bursting defect.
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