EXPERIENCE WITH CALCIUM TREATMENT OF STEEL

Sarbendu Sanyal, Mallikarjunarao P, Prabhat Kumar Ghorui, Devasish Mishra, S Manjini

JSW Steel Ltd., Bellary, INDIA – 583275
Corresponding author’s e-mail: sarbendusanyal@gmail.com

Abstract: Calcium (Ca) treatment is commonly used to control the shape and composition of oxide and sulphide
inclusions in aluminium (Al) and Al-Si killed steels. Calcium reacts with solid Al2O3 inclusions generating Ca-
aluminates of lower melting point which also got higher capacity to dissolve S resulting in the formation of Al2O3-
Ca-Mn sulphide compound inclusions. The addition of Ca must be optimum to produce only low-melting Ca-
aluminates that are liquid at steelmaking temperatures. Both too high or too low Ca affect the castability by the
formation of solid Ca-aluminates (CA6, CA2 and CA). In addition, higher Ca than required promotes the erosion
of Al2O3 containing refractories such as slide gate and SEN and also affects castability by the formation of CaS.
The optimum quantity of Ca that is to be added during Ca treatment depends on steel temperature, S, Oxygen (O2)
content and concentration of Al2O3 inclusions and therefore to be carefully controlled for successful inclusion
modification by Ca treatment. Success of Ca treatment also depends on efficient addition practices through wire
injection; an appropriate understanding is hence an essential prerequisite.
In the present investigation, an optimum regime for successful inclusion morphology modification by Ca
treatment was identified and implemented for better inclusion control. Excellent correlation in terms of inclusion
predictability was achieved from the developed Al-S-Ca matrix during actual plant trials. Successful
implementation of this Ca addition practice has enabled JSW steel plant to significantly improve the yield of
inclusion critical grades and enhance the customer satisfaction.

Keywords: Calcium treatment, Inclusion modification, Sulphide inclusion morphology

1. Introduction 2. Inclusion modification by Ca treatment

Inclusions in steel can form indigenously by Inclusion modification can be described by

deoxidation reactions or exogenously by external computing the reaction equilibria relevant to the
sources. Al when added to steel as deoxidant inclusion formation. Deoxidation and
generates Al2O3 inclusions which are hard, non- desulphurization reactions during Ca treatment of
deformable and tend to form clusters promoting Al killed steels are represented by equations (1) to
nozzle clogging during continuous casting. (5) and modification of Al2O3 inclusions by Ca
Therefore, Al killed steels are commonly treated into Ca-aluminates is given by equation (6)[1].
with Ca to modify solid Al2O3 inclusions into
liquid Ca-aluminates. Though, CaO and Al2O3 2[Al] + 3[O] = (Al2O3) (1)
can form different types of solid or liquid [Ca] + [O] = (CaO) (2)
inclusions at steel making temperatures, their [Ca] + [S] = (CaS) (3)
relative amounts, if controlled, ensure formation [S] + (CaO) = (CaS) + [O] (4)
of low melting compounds. Hence, the addition of 3(CaO) + 2[Al] + 3[S]= 3(CaS) + (Al2O3) (5)
Ca must be optimum to produce only liquid Ca- x
x[Ca] + (1 + 3) [Al2 O3 ] = (Al2 O3 . xCaO) +
aluminates at steel making temperature. 2x
3
Al (6)
Ca can also react with S forming CaS that reduces
the ability of Ca to modify Al2O3 inclusions. In practice, the total Ca to total Al ratio (Ca/Al) of
When S content of liquid steel is above 0.01%, the steel is commonly used as an indicator of the state
complete inclusion modification is difficult or of Ca-aluminate inclusions. However,
impossible[1]. S prevents Ca from reacting with Turkdogan[2] has indicated that this is a
Al2O3 due to the formation of CaS that finally misleading indicator as a part of Al is dissolved in
results into desulphurization. The steelmaker, steel and the remaining is present as inclusions.
hence, has to strike a balance between S, Al and Similarly, treated Ca is present either as fume or
Ca for efficient inclusion modification. as suspended particles in steel or slag. Thus, Ca/O
The present study reviews the principles of ratio is a better measure of state of Ca-aluminate
inclusion modification by Ca treatment along inclusions produced by the Ca addition[3].
with reviewing few application results achieved at However, the total O2 includes O2 in all forms
JSW Steel’s steelmelting shops. such as indigenous and exogenous inclusions. As
the quantification of their individual influence on
thermodynamics of Ca treatment is difficult, the
present study considered Ca/S ratio as the right
metric for the purpose.
2.1 Liquid Ca-aluminate inclusions:
Al, when added to liquid steel for deoxidation
purpose, reacts with O2 to form dendritic Al2O3
inclusions. Ca, during Ca treatment, initially
transforms into Ca vapour at steel making
temperature and dissolves into the liquid steel
during its travel from ladle bottom to top. This
dissolved Ca reacts with Al2O3 inclusions to form
Ca-aluminates.
morphology or sulfide shape control. At the end
of a successful Ca treatment, Al2O3 should get
modified into liquid Ca-aluminate and S should
get tied up as CaS which will dissolve and/or
precipitate on Ca-aluminates to form Ca-Al-O-S
globular type complex inclusion. CaS-MnS
precipitate on Ca-aluminates to produce desirable
bull-eye shaped inclusion (Fig.3) and floatation of
these inclusions is enhanced by bath stirring[5].

Ca modified globular Al2O3 inclusions, in liquid

form, impede cluster formation tendency and get
wetted by liquid steel and thus their removal from
steel is facilitated by bath stirring. The circled
region in the binary CaO- Al2O3 phase diagram as
shown in Fig. 1 shows the desirable composition
of liquid Ca-aluminate inclusions for successful
Ca treatment[4]. Undesirable solid Ca-aluminates,
formed as a result of over and under injection of
Ca, cause nozzle clogging during continuous
casting and as harmful as Al2O3 inclusions as far Figure 1 CaO-Al2O3 binary phase diagram [4]
as clogging is concerned.

2.2 Effect of S level:

Modification of Al2O3 inclusion is also affected

by high S level in the liquid steel as depicted by
Ca-Al-S ternary phase diagram[3] (Fig.2). Starting
from pure Al2O3 inclusions (point A), Ca content
increases in the inclusion up to a point, either B or
C, depending on the S content of the liquid, where
CaS formation starts. If S in the liquid is more
than 0.009%, inclusion chemistry follows the path
A-B-D, otherwise follows A-C-D route. As a
result, fewer inclusions actually achieve a Figure 2 Schematic representation of change in Al2O3
inclusion composition of Ca treated steel as a function
composition that falls within the liquid window
of S and Ca [3]
represented by C12A7 in case of high S liquid.
Thus, the goal of Ca treatment to produce liquid
Ca-aluminate inclusions, by following path the A-
C-D, can only be achieved by controlling S (and
Al) levels to the optimum values before Ca
addition.

2.3 Sulphide shape Control:

Ca-aluminate inclusions, retained in liquid steel,

suppress the formation of MnS stringers during
solidification as S get dissolved in liquid Ca-
aluminates to form Ca-Al-O-S globular inclusion.
This change in composition and mode of
precipitation of sulfide inclusions during
solidification of steel is known as sulfide
Figure 3 Al2O3 inclusion morphology modification by
Ca treatment [5]
The quantity of Ca addition and its addition
practice with reference to steel temperature and
composition, significantly influences the success
of the Ca treatment. The formation of solid Ca-

2
aluminates with unacceptable level of stringer
type sulphide inclusions in the final flat product
resulted from inefficient Ca treatment are
detrimental to the product properties. Therefore,
the process parameters like addition temperature,
level of total O2, S and Al in the steel bath should
be carefully controlled and the quantity of Ca
addition has to be optimized for successful
inclusion modification.

3. Development of Ca treatment norms: Figure 4 Effect of Al and S on liquid and solid Ca-
aluminates saturation limits[7]
Based on the wisdom of Ca treatment discussed
so far, it was felt prudent to develop simple but
effective norms for steel plant operators to
successfully achieve inclusion modification. The
following is a brief discussion on the development
of such norms at JSW Steel.

3.1 S level before Ca treatment:

As discussed, Ca treatment is not effective if the

Ca wire is added at higher S levels. A significant
amount of Ca is required to achieve low S levels
and such a reaction cannot proceed as excessive
Ca injection generates higher vapor pressure and
a reaction of Ca with O2 from air is favored over
a reaction with S[6]. This facilitates the formation
of CaO and precipitation of S as MnS inclusions
during solidification. Therefore, for inclusion
critical grades it is important to first reduce S level
to a low value by employing good slag and
controlled stirring before Ca wire addition.
Ca, when added to liquid steel in various forms
such as CaSi, CaFe, CaAlFe or pure Ca, converts
Al2O3 inclusions into Ca-aluminates as per the
reactions given in the equations (5) and (6), and
controlled by various parameters as already
discussed. The form of Ca-aluminates and their
stability as a function of Al and S at a typical Ca
addition temperature 1570 ⁰C is shown in Fig.4,
which is derived from the work done by Kor et.al.
[7]. Liquid Ca-aluminates of type 12CaO.7Al O
2 3
(C12A7) forms if S and Al falls below the line
represented by C12A7 whereas mixture of liquid
and solid Ca-aluminates forms above the line.
Solid Ca- aluminates of type CaO.Al2O3 (CA) are
stable above the line C12A7.
For effective inclusion modification, Ca is to be
added to steel after maintaining S and Al below
the line represented by C12A7 to achieve liquid
Ca-aluminates and to subside CaS formation. As
extensive study of the JSW Steel’s steelmaking
data had been taken up to establish Ca-treatment
parameters. This data, as superimposed in Fig.4,
confirm the above discussion.
Figure 5 Effect of Ca/S on sulphide inclusions
3.2 The Ca/S ratio:
Ca to S ratio (Ca/S) is considered as a significant
measure of steel cleanliness and needs to be
maintained more than a critical value for
successful Ca treatment[8,9]. In the present
investigation, Ca/S ratio based on tundish
chemistry is calculated for 13 higher and 39 lower
sulphide inclusion observed heats (Fig.5). Heats
with sulphide inclusion rating greater than 2.0 as
per standard IS 4163:2004 are considered as high
sulphide inclusion heats for this study. It is
observed from Fig.5 that heats with Ca/S ratio less
than 0.50 exhibited high sulphide inclusions in
HR coil. Therefore, it was established that
sulphide inclusions with higher rating would be
avoided if Ca/S ratio is maintained at greater than
or equal to 0.50.
3.3 The O2 level:
Figure 6 shows the effect of total O2 on the
amount of Ca needed to convert Al2O3 inclusions
into liquid Ca-aluminates at a S level of 100 ppm
at 1550 ⁰C temperature. Ca-S and Ca-Al
saturation lines are indicated for total O2 content
of 40 ppm. This indicates that the amount of Ca at
certain O2 and Al level should fall between
relevant Ca-S and Ca-Al saturation lines to form
liquid Ca-aluminates. When the total O2 content
is decreased from 40 to 30, 20 and 10 ppm the
window gets narrower and also the minimum

3
amount of Ca required for attaining the liquid Ca-
aluminates, for a constant Al content, decreases.
A total Al content of 200-400 ppm is considered
to be optimum based on the actual plant data to
achieve bath total O2 content of 25-35 ppm.
Higher bath S content at a constant temperature of
1550 ⁰C and total O2 20 ppm pushes the line
downward making the liquid Ca-aluminates
window narrower and increases the stability range
of CaS as shown in Fig.7; thus increasing the
difficulty in producing liquid Ca-aluminates.
Figure 6 Ca-aluminate & sulphide saturation lines
showing liq. window [1]
Therefore, through the present study, it was
established that the S content should be 60 ppm or
below before the Ca wire injection to achieve
liquid Ca-aluminates.
Figure 7 Same as Fig.6 with extrapolated liquid
window for different S levels.
3.4 Ca wire injection
The efficacy of Ca treatment depends on particle
size and different wire injection parameters. It
was reported that particle size in the range of 200
to 700 µm works best for the Ca treatment to
avoid very high and low rates of reactivity[6].
Ca is generally added to steel in the form of Ca
silicide or ferrocalcium by cored wire injection
method. It is imperative to control the wire
feeding rate in such a way that the Ca powder is
released at the bottom of the ladle and consumed
by the melt to the maximum extent in order to
make this cored wire injection process efficient
and cost effective. A separate study[10] on Ca wire
injection parameters and their influence on Ca
recovery was referred to establish the norms to
achieve effective inclusion modification for
efficient Ca wire injection.
4. Conclusions
The challenge posed by Al, S and O2 content of
the steel on inclusion modification through Ca
treatment and the significance of the ratios
between these elements were discussed.
The desired S level to produce low melting Ca-
aluminate and that to control sulphide shapes have
been established.
A processing window consisting of Al, S, Ca and
O2 at typical Ca addition temperature 1570 °C
was developed and successfully validated with
the plant data.
Finally, wire injection parameters were referred to
aid efficient Ca treatment.
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