T.

LIS ISSN 0543-5846

METABK 48(2) 95-98 (2009)
UDC – UDK 669.787:549.5.001.43:669.775:539.5.001.43:669.891=111

MODIFICATION OF OXYGEN AND SULPHUR

INCLUSIONS IN STEEL BY CALCIUM TREATMENT
Received – Prispjelo: 2008-06-22
Accepted – Prihva}eno: 2008-10-15
Preliminary Note – Prethodno priop}enje

In the article, the results of examinations of changes in deformability of oxygen and sulphur inclusions in struc-
tural steel processed with calcium are discussed. The results obtained imply the positive influence of the cal-
cium additives on the changes in geometry of oxygen and sulphur inclusions related to the modification of
their chemical composition.
Key words: modification, oxygen and sulphur inclusions, calcium treatment, deformability
Modificiranje kisikovih i sulfidnih uklju~aka u ~eliku obradbom kalcijem. U ~lanku se raspravljaju rezul-
tati istra`ivanja promjena deformabilnosti kisikovih i sulfidnih uklju~aka u strukturalnom ~eliku obradbom kalci-
jem. Dobiveni rezultati ukazuju na pozitivan utjecaj dodataka kalcija na promjenu oblika kisikovih i sulfidnih
uklju~aka sukladno njegovom kemijskom sastavu.
Klju~ne rije~i: kisikovi i sulfidni uklju~ci; modificiranje, obrada kalcijem; deformabilnost

INTRODUCTION ides are more stable than sulphides [1]. If calcium is to

react with sulphur and not with oxygen then the oxygen
The non-metallic inclusions are inevitable conse- activity in a liquid steel at the temperature of 1873 K
quence of metal elaboration processes and are foreign should be about 19 times lower than sulphur activity [2],
phases always present in solid and liquid metal. The inclu- that is a very difficult condition to achieve.
sions have a different shape and a size from several to sev- Consequently, it is presumed that the first reaction
eral hundred micrometers (in diameter). They are ran-
after calcium is introduced in to the liquid steel is the
domly distributed in the matrix of the base metal and form
calcium oxidation.
a dispersion phase in liquid and in solid metallic phase.
The CaO-Al2O3 system [3] shows the possibility of
The non–metallic inclusions may directly affect the
occurrence of calcium aluminates a series with different
functional properties of metals, especially steel which is
melting temperature and only one of them, i.e.
commonly used constructional material. The reducing
the contents of non-metallic dispersion particles in the 12CaO·7Al2O3 is in a liquid form at liquid steel temper-
metal and the introducing of modification process are ature. The following oxides may be liquid also:
significant methods for their decreasing the unfavour- – C12A7 – melting point 1728 K
able effects. The modification is a process of adding to a – C12A7-CA – melting point 1673 K
metal bath a small amount of substance (i.e. a modifier) – C3A- C12A7 – melting point 1663 K.
which changes the physical-chemical properties of in- As well as the following ternary eutectics:
clusions. The modifiers are metallic substances that – 62 % SiO2; 23,25 % CaO; 14,75 % Al2O3 – melt-
change the solid oxide and sulphide particles steel bath ing point 1438 K;
to liquid inclusions in liquid metal. – 42 % SiO2; 38 % CaO; 20 % Al2O3 – melting point
In this paper the results of modifications of oxide and 1538 K;
sulphide inclusions in steel with calcium, especially in – 40 % SiO2; 49 % CaO; 11 % Al2O3 – melting point
respect of change in theirs shape and deformability are 1538 K.
presented and discussed. On the basis of our results it is concluded that the
modification of Al2O3 particles with calcium is achieved
MODIFICATION OF OXIDE only for the CaO content in these particles is in the range
AND SULPHIDE INCLUSIONS of 25 % to 60 %.
Sulphur belongs to a group of elements which exhibit
The chemical affinity of calcium to oxygen is higher almost unlimited solubility in a liquid iron [4]. During the
than that to sulphur and at the temperature of 1873 K ox- solidifi-cation sulphur is selectively deposed at grain
Teresa Lis, Faculty of Materials Science and Metallurgy, The Silesian boundaries producing characteristic steel defects. Sul-
University of Technology, Katowice, Poland phur is found at grain boundaries in form of various

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 T. LIS: MODIFICATION OF OXYGEN AND SULPHUR INCLUSIONS IN STEEL BY CALCIUM TREATMENT

sulphides or theirs solutions, depending on the chemical

composition of steel. The sulphides which have the most
negative influence on steel properties are the sulphides of
type II and III. These sulphides grow in length at plastic
working (particularly hot working) and cause a heteroge-
neity of mechanical properties of final products.
The purpose of introducing calcium to a metal bath is
a change of the sulphur release mechanism in such a way
that the sulphur is bound to oxide or aluminate particles
and not deposed as sulphide inclusions at grain bound-
aries during the steel solidification.

EXAMINATIONS
The previous researches reveal that constructional
steels are very sensitive to non-metallic inclusions. Cur-
rently, it the application of such steel for the production
Figure 1. The sulpho-oxide inclusion; 1 – calcium alumi-
of elements which feature uniaxial symmetry e.g. bolts nate, 2 – sulphide (Ca,Mn)S
and shafts is investigated. A very important issue is the
machining, especially the process of tool wear and the
mechanism of chip formation [5, 6]. New technological
solutions are being searched with the aim to change the
chemical composition, deformability of non-metallic
particles and achieve their a more advantageous distri-
bution in steel.
Thermodynamic analysis [7, 8] shows that in alu-
minium-killed steels, the solid particles of alumina or
hercenite are formed that form clusters. After the cal-
cium is introduced, heterogenic reactions of calcium
aluminates formation take place on the surface of the ox-
ide particles previously formed. The small activity of
oxygen and sulphur enables the modification of oxide
inclusions to calcium aluminates. For increasing sulphur
contents, the range in which oxides are modified by cal- Figure 2. The sulpho-oxide inclusion; 1 – Al2O3, 2 – MnS
cium is narrowing as result of the increased formation of
– area fraction of particles (AA),
calcium sulphide [8].
– distribution of number and area fraction of
In the investigation a carbon construc-tional steel
non-metallic particles,
was used. The modification was peformed with the cal-
– shape coefficient value of non-metallic particles.
cium alloy CaSi (30 % Ca) that was introduced into steel
The microscopic examinations proved that in steel
in form of core wire into the ladle of volume of 20 Mg.
samples treated with calcium, the most numerous inclu-
The samples of metal were examined 20 minutes after
sions are oxide-sulphides with an oxide core of the
the addition of calcium. Ten test melts were treated: two
Al2O3-MgO-CaO system. The calcium aluminates are
without calcium treatment and the remaining ones with
of different shape and have a lower content of calcium.
diverse calcium addition. Most of aluminates had a sulphidic ring of type
The aim of experiments was to evaluate the modifi- (Ca,Mn)S – Figure 1.
cation with calcium of non-metallic dispersion phase in The form of sulphides forming the inclusions case
steels of various aluminium, calcium and sulphur con- and their chemical compositions depend on the content
tents - represented as Ca/Al and Ca/S. The melts without of sulphur and calcium in steel. By low calcium content,
calcium additives were marked as O1 and O2. The melts the main coating component is MnS – Figure 2.
in which Ca/Al lower than 0,09 were marked as A1÷A3; With the increase of the content of calcium in steel
the melts in which Ca/Al is within the range 0,09÷0,14 also its content in the surface ring increases up to the
were marked as B1÷B3, whereas the melts of Ca/Al > point of formation of CaS (Figure 3).
0,14 were marked as C1 and C2. The quantitative evaluation has been performed with
The assessment of non-metallic particles, their chemi- Morphopericolor picture analyser and the evaluation of
cal composition, distribution, size and shape was carried inclusions on 50 field of view of each separate
out with using the following metallographic methods: microsection has been made. The analysed area was of
– number of particles per 1mm2 (NA), 2,349 mm2.

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 T. LIS: MODIFICATION OF OXYGEN AND SULPHUR INCLUSIONS IN STEEL BY CALCIUM TREATMENT

The analysis of a number and the area fraction of

non-metallic particles indicate
a positive influence of the treatment of steel with cal-
cium. In all of the tested samples after the CaSi treat-
ment the number and area fraction of plastic and
non-plastic particles were lower.
The results of examination, i.e. number, area fraction
and shape coefficient of non-plastic particles show that
the calcium treatment effects do not depend on the vol-
ume of the Ca addition within the range analysed of
Ca/Al = 0,0247÷0,0350 (Table 1).

Table 2. The results of quantitative evaluation of pla-

stic of non-metallic inclusions.
Number of Area fraction Mean Shape
non-metal- of non-meta- area of coeffi-
Figure 3. The sulpho-oxide inclusion; 1 – oxide like Melt
lic particles, llic particles, particles cient /
Ca/S
2Al2O3-MgO, 2 – CaS (NA) / mm-2 (AA) / % / mm2 x
O1 109 0,071 9,80 0,37 -
The shape coefficient of particles in non-metallic dis-
persion phase was calculated using to the dependence: O2 270 0,085 4,42 0,42 -

4 × p× a A1 156 0,050 5,25 0,39 0,262

x=
l2 A2 127 0,027 5,36 0,44 0,300
where: a - the area of measured particle in mm2 and l A3 78 0,021 2,87 0,53 0,087
- perimeter of a measured particle in mm. B1 222 0,038 2,54 0,49 0,250
The examinations based on quantitative metallogra- B2 120 0,012 1,04 0,63 0,350
phy have been conducted on crosswise microsections of B3 161 0,026 1,09 0,54 0,550
samples taken from rolled ingots.
C1 76 0,007 0,72 0,58 0,757
The non-metallic particles in the tested steel have
C2 89 0,008 0,42 0,63 1,167
been divided into two groups. According to the results of
analyses (electron microprobe) it has been decided that
Comparing the results obtained with the melts without
the oxide and oxide sulphides particles achieve the maxi-
calcium treatment, it is worth to mention that the area
mal value of elongation (the value of Feret’s diameters ra-
tion Fx /Fy) of 2 these particles were considered as fraction of non-plastic particles decreases within the ran-
non-plastic; sulphides the elongation was higher than 2 ge of 0÷66 %, the mean area decreases only slightly
therefore, they have been considered as plastic particles. (4÷33 %) while the increase of the shape coefficient val-
Table 1 and Table 2 presents the results of quantita- ues is in the range of 0,73 to 0,85. The addition calcium
tive assessment of non-metallic inclusions (Table 1 – for aluminium-killed stells causes globularisa-tion of par-
non-plastic particles, Table 2 – plastic particles). ticles as well as their inconside-rable breaking up. The
best result were obtained for melt B2 with Ca/Al = 0,112.
In comparison with steels without the calcium treat-
Table 1. Results of quantitative assessment of ment the addition of calcium for aluminium-killed steels
non-plastic of non-metallic inclusions. in the amount which enables obtaining Ca/S < 0,7 leads
Number of Area fraction Mean Shape to. The decrease of the area fraction, mean area and in-
Melt
non-meta- of non-meta- area of coeffi-
Ca/Al crease of shape coefficient of plastic particles. For Ca/S
llic particles llic particles, particles cient /
(NA) / mm -2
(AA) / % / mm 2
x
> 0,7 the number of plastic particles is decreased by ca.
55 %, the area fraction by ca. 90 %, the mean area by
O1 1265 0,226 1,09 0,74 -
more than that and value of shape coefficient is in-
O2 861 0,175 0,98 0,73 -
creased by ca. 50 % are found. Such a decrease of the
A1 614 0,086 1,05 0,81 0,089 number, the area fraction and the mean area of plastic
A2 1184 0,231 1,01 0,79 0,039 particles proves the positive influence of calcium treat-
A3 490 0,074 0,85 0,78 0,027 ment on the steel cleannes, whereas the increase of the
B1 905 0,149 0,94 0,78 0,100 shape coefficient proves the globularisation of other
B2 1439 0,174 0,68 0,85 0,112 particles remaining in the steel.
B3 586 0,077 0,73 0,79 0,095 In the following figures, the distributions of the area
C1 543 0,098 0,94 0,81 0,165
fraction and number of non-metallic inclusions with re-
gard to their shape coefficient (Figure 4), elongation
C2 820 0,127 0,87 0,81 0,350
Fx/Fy (Figure 5) and length (Figure 6) is shown.

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 T. LIS: MODIFICATION OF OXYGEN AND SULPHUR INCLUSIONS IN STEEL BY CALCIUM TREATMENT

– a decrease of the number of long non-metallic par-

ticles (Figure 6). A considerable decrease of the
number of inclusions of the length below 0,7 mm
has been attained for melts A3, B1÷B3 and C1, C2,
and the largest one for melts C1 and C2, where no
inclusions longer than 0,5 mm have been found.
One of the two steps could be the rate-controlling for
the interaction between the liquid calcium aluminate
and solid alumina: (1) calcium diffusion in the liquid
calcium aluminate layer, or (2) the chemi-cal reaction at
the alumina/calcium alumi-nate interface. If the rate is
controlled by the calcium diffusion in the liquid product
Figure 4. Distributions of the area fraction of non-metallic
layer there should be a significant calcium concentration
inclusions with regard to their shape coefficient.
gradient in the liquid product layer [9, 10].

CONCLUSIONS
The calcium treatment of aluminium-killed steels
leads to the modification of non-metallic inclusions and
the change of their chemical composition and plastic
deformability. Based on the results of the examinations
presented, the following conclusions are drawn:
1. In aluminium-killed steel treated with calcium, the
most numerous inclusions are oxide-sulphides
with an oxide core and a sulphide surface layer.
2. The addition of calcium to the steel has a positive
influence on the steel cleannes by decreasing the
Figure 5. Distributions of the area fraction of non-metallic
inclusions with regard to their elongation Fx/Fy. number and area fraction of non-metallic inclu-
sions.
3. The addition of calcium to the steel in an amount
ensuring that Ca/Al>0,14 and Ca/S>0,7 leads to
considerable decrease of the number and area
fraction of long inclusions as well as their high
plastic deformability.
4. The addition of calcium to the aluminium-killed
steel has a positive influence on globularisation
of other inclusions remaining in steel.

REFERENCES
Figure 6. Distributions of the number of non-metallic in- [1] Gaye H., Gatellier M., Nadif M., Riboud P.V.: Revue de
clusions regard to their length in the tested con- Metallurgie – CIT, 84 (1987) 11, 759-771.
structional steel. [2] Lis T.: Metallurgy and Foundary Engineering, 28 (2002) 1,
29-45.
The results provided indicate that the calcium treat- [3] Salter W.J.M., Pickering F.B.I.: Iron Steel Inst., 207 (1969)
ment of aluminium-killed steels leads to: 992-1002.
[4] Dahi W.: Stahl u.Eisen, 971(977)8,402.
– a decrease of area fraction of particles character-
[5] Pytel St.: IV Int.Conf.Stereology and Image Analysis in
ised by the lowest values of the shape coefficient Material Science, 3-6.10.1994, p.363.
(Figure 4). The best results were obtained for [6] Dodd B., Bai Y.: Academic Press Inc. London LTD, 1987,
melts C1 and C2 (Ca/Al>0,14 and Ca/S>0,7); be- p.263.
low the level of 0,4 of shape coefficient no inclu- [7] Lis T.: Archives of Metallurgy, 39 (1994) 2, 155-192.
sions have been found; [8] Lis T., Ró¿añski P.: Hutnad 75 (2005) 5, 259-264.
– a decrease of area fraction of particles of the larg- [9] Lis T.: Habilitation Thesis, Scientific Booklets Metallurgy,
The Silesian University of Technology, 49,1995.
est elongation of Fx/Fy (Figure 5). The best results
[10] Han Z., Lind M., Holappa L.: Int.Conf. on Non-metallic
have been obtained for melts C1 and C2 Inclusions Control, Stal 2004, 5-6 May 2004, Sweden, p.13.
(Ca/Al>0.14 and Ca/S>0,7), where inclusions of
elongation exceeding 3,0 have not been found; Note: The responsible translator for English language is the author T. Lis.

98 METALURGIJA 48 (2009) 2, 95-98