Clean Steel Technology LD SHOP 1

The term "clean steel" is commonly used to describe steels that have low levels
of the solute elements sulfur, phosphorus, nitrogen, oxygen and hydrogen;
controlled levels of the residual elements copper, lead, zinc, nickel, chromium,
bismuth, tin, antimony and magnesium; and, a low frequency of product defects
that can be related to the presence of oxides created during the act of steel
making, ladle metallurgy, casting and rolling.

Clean steels are steels with a low frequency of inclusions of average diameter
less than 5 microns.

The major problems in clean steel manufacture are

• incomplete separation of clustered solid inclusions (> 5 microns in diameter)

• the presence of sporadic larger liquid inclusions due to emulsification of
covering slags
• the presence of solid materials that originate from the refractories used to reline
the ladles / tundish.
Clean Steel Technology LD SHOP 1
Clean steel making and casting practices are based upon the following principles:

• Deoxidation - Oxygen, which is dissolved in liquid steel at the steel making and
melting stage, must be transformed into a solid or a gas and removed before
casting.

• Deoxidation Product Removal – Deoxidation products like Alumina,

Manganese Silicates, Calcium Aluminates etc must be removed through physical
or chemical means

• Prevention of Reoxidation of the Steel - The external oxygen sources, which

are responsible for the reoxidation of liquid steel, must be eliminated at every
step in the process.

• Inclusions Originating From Emulsification of Slag - The physical

entrapment of the fluxes used during steel refining and casting must be
eliminated.

• Inclusions Originating From Refractories - Refractories in contact with liquid

steel must be chemically stable and resistant to corrosion and erosion.
Clean Steel Technology LD SHOP 1
The inclusions formed in steel can be broadly classified as
1) Micro Inclusions - Micro-inclusions are formed due to reactions between
alloying additions and oxygen in liquid steel. Their formation is generally either
heterogeneous or from highly superstatuated areas during alloy addition. Due to
the nature of formation of these inclusions (nucleation and growth) they are
generally small (less than 5 microns) unless they agglomerate due to turbulence
or grow under conditions of high oxygen flux. In this study we will define micro-
inclusions as those inclusions with diameters less than 20 microns. In addition we
will define them to have diameters greater than 1 micron

2) Macro inclusions – Macro inclusions are the inclusions which are formed over
and above the deoxidation of the steel and are typically dependent on the steel
making practice and conditions. These may be due to
1) Reoxidation of steel
2) Vortexing of slag into the mould
3) Inclusions from external sources such as refractories
4) Excessive purging leading to entrainment of slag into the steel
5) Falling of clogging deposits
These are typically larger than 20 microns
Clean Steel Technology- Micro Inclusions LD SHOP 1

The formation of inclusions during steel making is inevitable as oxygen is more

soluble in liquid iron than in solid iron.

In addition, at 1600 C and gas phase oxygen partial pressures greater than 6 x
10-9 atmospheres, liquid iron will spontaneously oxidize to liquid iron oxide.

The saturation limit for oxygen in liquid iron in contact with iron oxide at 1600
C is 0.23 wt%, a value that decreases with temperature according to the
equilibrium between iron, oxygen and iron oxide.

The solubility limit for oxygen in solid iron is low and the partial pressure of
oxygen in equilibrium with solid iron and iron oxide at 1000 C is 1 x10 -15 atm.

Thus, if a pure liquid iron sample in equilibrium with FeO is solidified and
cooled, iron oxide would precipitate interdendritically as spherical liquid iron
oxide inclusions
Clean Steel Technology- Micro Inclusions LD SHOP 1
The practical limit of steel cleanliness in normal steels is set by chemical
equilibrium and, to reach this value, all inclusions formed during the deoxidation
reaction must be separated before solidification .

In steels deoxidized with silicon and manganese, the equilibrium is set by the
formation of a liquid manganese silicate;

In aluminum killed steels, by the formation of solid alumina;

In calcium treated, aluminum killed steels by the formation of a liquid calcium

aluminates.

To further reduce soluble oxygen content at a given temperature, manganese silicate

or alumina can be dissolved into a slag. For example, dissolution of alumina into a
slag can result in the soluble oxygen content of an aluminum-killed steel being
reduced to less than 2 ppm. Dissolution of silica into a slag of calcium aluminates,
for example, can significantly reduce the activity of silica and lead to soluble
oxygen contents of silicon killed steels in the range of aluminum-killed steels.

THEREFORE IT IS IMPORTANT TO KILL THE SLAG

Clean Steel Technology- Micro Inclusions LD SHOP 1

The use of chemical equilibrium to reach low soluble oxygen contents is

widespread; however, to be effective, all phases in contact with the liquid steel
must be at the same equilibrium condition.

If aluminum killed steels are at equilibrium, reaction must also be at equilibrium;

therefore, FeO activity in slags must be very low or aluminum will oxidize by
reaction with the slag.

Similarly equilibrium MnO and SiO2 slag activities in the slag are uniquely set
by the addition of aluminum and any increases above the equilibrium slag levels
will result in reaction with the slag and the formation of alumina.

Therefore, in practice, the slag systems must be designed to be very low in FeO
and MnO after the steel has been killed. LD slags tend to be high in FeO and
MnO and this has led to the development of slag-free tapping techniques and,
also, slag killing using calcium carbide or aluminum.
Clean Steel Technology- Micro Inclusions LD SHOP 1

Clustered Alumina inclusions Semi Clustered Alumina

inclusions
Clean Steel Technology- Micro Inclusions LD SHOP 1

Globular dual phas micro inclusions

Clean Steel Technology- Micro Inclusions LD SHOP 1

Clustered Alumina inclusions Semi Clustered Alumina

inclusions
Clean Steel Technology- Macro Inclusions LD SHOP 1
- Refractories
Equilibrium between the refractories and the steel must also be considered. For
example, high alumina refractories are not 100% alumina and numerous binders
are added which can contain oxides that are less stable than alumina. Under these
conditions the ladle refractories will react with the liquid steel, if not adequately
designed.
Clean Steel Technology- Macro Inclusions LD SHOP 1

Inclusions due to refractory wear

Clean Steel Technology – Macro Inclusions - LD SHOP 1
Interaction between Liquid Steel and Liquid Slag

Liquid inclusions can occur due to deoxidation/reoxidation reactions in

manganese-silicon killed steels or in calcium treated, aluminum killed steels.
These inclusions tend to be less than 10 microns in diameter and are rarely
problematic. Larger liquid inclusions (10 to 300 microns) occur due to
entrainment of the covering slags that are present on top of liquid steels and are
generally due to practice related issues

There are five processing conditions where emulsification can be expected:

• Slag metal interaction in the ladle or the tundish after the steel has been treated
• Vortexing in the ladle or the tundish while emptying out
• Very violent purging
• Level fluctuations in the mould leading to casting powder entrainment
Clean Steel Technology- Macro Inclusions LD SHOP 1

Inclusions due to entrainment of slag

Clean Steel Technology – Macro Inclusions LD SHOP 1
- Reoxidation
Reoxidation is probably the most common cause of macroinclusion formation
in casting . To understand reoxidation one must understand that liquid iron is
not stable in the presence of oxygen and that the spontaneous reaction that
occurs leads to the formation of iron oxide.
As deoxidizers are added the steel remains unstable in the presence of oxygen
as a gas but now the inclusions which form include the oxides of the
deoxidants. Some deoxidants, notably aluminum, magnesium and calcium,
form very stable oxides which are more stable than some slag chemistries and
some refractory chemistries. In this circumstance the steel reacts with the less
stable oxides. The reoxidation can occur by reaction with:
•The ambient atmosphere (air)
•The slag components less stable than the oxide of the deoxidant
•The refractories which are less stable than the oxides of the deoxidant
Clean Steel Technology- Macro Inclusions LD SHOP 1

Inclusions due to reoxidation

Clean Steel Technology – Macro Inclusions LD SHOP 1
- Inclusion agglomeration due to clogging
The formation of clogs when steels containing solid inclusions are cast can result in
quite large macro- inclusion defects if the clogs are released during teaming.
Clogging of pourng nozzles can be the source of large macro-inclusion defects
when steels are dirty.
1) All solid inclusions tend to agglomerate due to surface tension effects
2) Zr, Ti Al and the rare earths are all refractory at steelmaking temperatures and
caused clogging. However, this is not the case with Si + Mn as a deoxidizer
3) Two different forms of alumina exist in the case of an Al-killed steel. One
consisting of chalky alumina which is a powdery white substance and the other
consisting mainly of metal containing a large number of alumina clusters.
4) Supersaturation of Al and O in steel leads to a high speed growth of alumina.
High speed growth is characterized by dendrites and needles and occurs
because the supply of reactants causes morphological instability in the growing
dendrites.
5) Ti added and Al-killed steel (Ti-AK) form inclusions which are coarse and
granular which differed from the dendritic alumina in Al-killed steel.
Clean Steel Technology LD SHOP 1

The final level of cleanliness is a balance between the rate of inclusion removal and
the rate of inclusion formation. Clearly to refine liquid steel the rate of removal
must be greater than the rate of creation; therefore, reductions in the rate of reaction
between the steel and the slag and the steel and the refractory system will enable the
lowest possible inclusion contents in the shortest processing time. Reoxidation of
liquid steel by reaction with air causes very high rates of inclusion formation and,
often, causes the rate of formation of inclusions to be greater than the rate of
inclusion removal. Thus, a natural limit to any process that enables inclusion
removal is the point at which air reoxidation begins.
Keys to the Production of Clean Steels LD SHOP 1
If the goal of clean steel manufacture is to produce steels with a low frequency
of inclusions with diameters less than 5 microns, then the following steps must
be followed:
        Reoxidation must be eliminated
        Removal of primary deoxidation inclusions must occur in the ladle
        Inclusion agglomeration must be eliminated after treatment
        Processing after the ladle must not contribute to cleanliness problems and
should be designed for further inclusion removal to allow clustered inclusions
and inclusions that precipitate due to a temperature decrease to completely
separate from the liquid steel.
        Slag emulsification must be eliminated as liquid inclusions of the size
range that is found in liquid steels due to emulsification ( 20 to 300 microns) are
very difficult to remove from liquid steels.
Inspite of all the care taken at different stages some inclusion
will remain or will get generated .We should be able to modify inclusions
remaining in the steel such that they do no cause nozzle clogging
Nozzle Clogging LD SHOP 1

Clogging occurs due to three types of inclusions:

(1) Alumina-~Al2O3
(2) Calcium sulfide - CaS
(3) Spinel- MgO-Al2O3
These are the enemy! All these inclusions are solid at steelmaking temperatures and will
build up on the refractories and cause clogging of the nozzle area or tundish gates

The goal of good castability practices is to reduce these inclusions enough to have good
casting with no large inclusions breaking off into the steel. Note that modification of
all the inclusions to a liquid form might not be necessary. Good castability can be
achieved, even when a portion of the inclusions is solid or semisolid.
Nozzle Clogging - Alumina LD SHOP 1

Nozzle blockage by aluminum-deoxidized steels is associated with the precipitation

and agglomeration of alumina in the nozzle bore

Oxide-type inclusions precipitate from solution due to a change in the oxide

solubility product with decreasing temperature and the inclusions form and
precipitate in the nozzle bore where the temperature decrease is the most
pronounced.

Any deoxidizer which forms a solid oxide phase at steelmaking temperatures can
produce nozzle blockage.

The mechanism of nozzle blockage postulated by researchers are

1) The build-up of alumina in nozzles can be attributed to reoxidation and deoxidation.
2) Reduction of the silica in the refractory nozzle by the aluminum in the steel,
3) Diffusion of the oxygen through the pores of the nozzle producing oxidation of the
aluminum in the steel,
4) Alumina deposition due to boundary layer flow.
Nozzle Clogging - Alumina LD SHOP 1

The simplest solution to nozzle blockage is a chemical one in which the melting
temperature of the oxide produced by the strong deoxidizer would be lowered below
that of the steel

Modification of the indigenous inclusions by calcium can minimize and even eliminate
the nozzle blockage problems characteristic of aluminum-killed steels

In calculated inclusion precipitation diagram for the Fe-O-Ca-Al system, the relative and
not absolute amounts of calcium and aluminum determine the identity of the calcium
aluminate inclusion phases

To produce the necessary conversion of the indigenous inclusions from alumina to the
requisite calcium aluminate phases, the calcium concentration in the liquid steel
should probably exceed 0.10 – 0.14 times the aluminum content.

Contamination of the steel by magnesium, however, may inhibit the calcium effect
Nozzle Clogging – Ca – Al Phase diagram LD SHOP 1
Nozzle Clogging – Effect of Ca LD SHOP 1

Nozzle precipitate of Al2O3

is seen when the Ca/Al ratio
is < 0.007
Nozzle Clogging – Effect of Ca LD SHOP 1

Nozzle precipitate of
CaO.6Al2O3 . In addition,
there is a 14% increase in
inclusion volume when
CaO.6Al203 forms instead of
Al203*. As a result, the
severity of the nozzle blockage
increases when small amounts
of calcium are added to
aluminum-deoxidized steels
and the CaO.6Al203 inclusion
phase forms instead of Al203
Nozzle Clogging – Effect of Ca LD SHOP 1
The nozzle flow properties of the
aluminum deoxidized steels did not
improve until the ratio of the calcium
and aluminum contents in the tundish
exceeded 0.115 severe blockage was
eliminated and when the ratio
exceeded 0.14, the tundish drained .
The nozzle precipitates show Nozzle
precipitate of CaO.6Al2O3 (major) +
CaO.2Al2O3.
Nozzle Clogging – Effect of Ca LD SHOP 1
In case of a Ca/Al ratio
of 0.12 to 0.13 the
nozzle precipitates
show CaO.2Al2O3 and
the casting was with
minimal blockage
Nozzle Clogging LD SHOP 1

It can be seen from this

graph that the castability
dramatically increases
beyond 0.10 Ca/Al ratio
Nozzle Clogging – Effect of Ca LD SHOP 1
This graph shows the Ca requirement
in steel to ensure maximum flow ability
of steel at different Ca levels
However there are other
considerations like the high cost of Ca
as well as the attack of Ca on the ladle
refractories as well as the stopper and
SEN. As such even though literature
recommends a Ca/Al ratio > 0.14 ,
most steel plants try to maintain a
Ca/Al ratio of 0.10 – 0.14
This ratio can be the ratio of Ca added
in kg/Total Al added at all stations in
kg
Or
For ease of understanding , this can be
the Ca/Al ratio in the LF out steel
Calcium Requirements for maximum flow
ability of steel
Nozzle Clogging – Spinels LD SHOP 1

One of the observations made, based upon scanning electron microscope

analysis of the samples in the above study, was that the "majority of aluminate
inclusions contained varying amounts of magnesium
Modification of the magnesium aluminates by calcium is less effective than the
modification of pure aluminates. The magnesium may originate from the
aluminum used for deoxidation or from the ladle lining.
As the oxygen activity decreases, the rate of reduction of MgO from the
refractories increases, as does the magnesium in solution.
Nozzle Clogging – Spinels LD SHOP 1
Both the aluminum and
magnesium in solution in
the steel decrease as the
basicity (lime-to-silica
ratio) decreases. The
greatest decrease in these
two elements occurs
between a basicity of 1.4 to
1.1 and, at the same time,
the oxygen activity in the
steel increases . This is bad
for desulphurisation but
good for avoiding spinels
 Nozzle Clogging – Al – Ti Inclusions on LD SHOP 1
Castability of Steel The best option for Ti-
containing Al-killed steel
is to eliminate chances of
0.1

Ti2O3 Al2O3.Ti2O3
reoxidation to the extent
possible. Since the Al-
killed steel contains
TiO2 IF steel
<5ppm [O], oxidation of
Ti causes formation of
Ti2O3, and not TiO2. In
0.01

Al2O3.TiO2 TiOX
case the steel is not fully
killed, i.e. if [O] > 20
ppm, TiO2 inclusions may
Al2O3
start forming, in place of
O = 20 10 ppm 5 ppm Ti2O3(point E). Co-
0.00
1

0.0001 0.001 0.01 oxidation in such case can

[Al]steel (%) form
Al2O3.TiO2inclusions.

Least problem Moderate problem Worst problem

 Deoxidation LD SHOP 1

Oxide inclusions in steel have two major sources: chemical reaction and emulsification.
The natural oxide inclusions are a response of the liquid steel to the chemicals which
are added as alloying elements. The emulsified inclusions are due to the interaction of
shear forces between two liquids or between a liquid and a solid and are tend to be
larger than the natural inclusions found in liquid steels. Given significant time the
thermodynamically most stable inclusion will become the natural inclusion of the
system. In the section the thermodynamically stable inclusion will be documented for
steels that are deoxidized with manganese, silicon, aluminum and calcium
Deoxidation LD SHOP 1
Deoxidation With Silicon - Manganese:
The following reactions occur when silicon and manganese are added to a liquid
steel:

[Si] + 2 [O] = SiO2 ...(1)

[Mn] + [O] = MnO ...(2)

Where brackets indicate elements dissolved in steel. The deoxidation product will
be either molten manganese silicate or solid silica depending on the amount of
elemental addition. The overall reaction for Si-Mn deoxidation is given by

[Si] + 2(MnO) = 2[Mn] +(SiO2) ...(3)

Log K = (1510/T) + 1.27 ...(4)

The equilibrium state for Si/Mn deoxidation has been calculated using the free
energy of above reaction and thermodynamic data on the activities of Si and Mn in
steel and the activities of MnO and SiO2 in molten silicates.
Deoxidation LD SHOP 1

Figure 1. : Equilibrium relations for deoxidation of steel with

silicon and manganese at 1600oC.
Deoxidation LD SHOP 1

Figure 1. : Equilibrium relations for deoxidation of steel with

silicon and manganese at 1600oC.
Deoxidation LD SHOP 1
The silicon and manganese concentrations are generally adjusted such that the
deoxidation products are liquid manganese silicate in order to avoid nozzle
clogging.

Semi-killed steels are also made by deoxidising the steel in the tap ladle with
addition of a small amount of Al together with silicomanganese or a
combination of ferrosilicon and ferromanganese.

In this case, the deoxidation product molten manganese aluminosilicate. For

the deoxidation product MnO - Al2O3 - SiO2 saturated with Al2O3, the silica
activities are 0.27 at 1650oC, 0.17 at 1550oC and 0.12 at 1500oC. Using this
data and equation (1), the deoxidation equilibria are calculated for A/Si/Mn
killed steels. The results are shown in Figure 2 and compared with Si/Mn
deoxidation. These calculations are for steels with very low soluble aluminum
contents (less than 0.005 wt pct Al) and indicate the lowest oxygen content that
can be achieved aluminum without precipitating alumina under these
conditions. Higher soluble aluminum contents (above 0.005 wt pct Al) will
lead to the precipitation of solid alumina as the natural inclusion, regardless of
the manganese and silicon contents.
Deoxidation LD SHOP 1

Deoxidation equilibria with Si/Mn compared with Al/Si/Mn for the deoxidation
product saturated with Al2O3
Deoxidation LD SHOP 1
Deoxidation with Aluminum: The following reaction occurs when Al is added to
steel.

2[Al] + 3[O] = Al2O3(s) (5)

Log K = - (62680/T) + 31.85 (6)
The equilibrium between pure alumina and Al in liquid steel is well known. The
amount of dissolved oxygen at different Al contents and temperature is shown in
Figure 3. When the Al killed steel is treated with Ca the natural inclusion becomes
calcium aluminate and a decrease in the soluble oxygen content of the steel results
as shown in Figure 3.
Deoxidation LD SHOP 1

Deoxidation with aluminum in equilibrium with Al2O3 or molten calcium aluminate

with CaO/Al2O3 = 1.1