Inclusion Control for Clean Steel

SANTOSH KUMAR
MGR(SMS)
NINL
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 Contents
1. Introduction
2. Inclusion assessment
3. Inclusion Source & Control
4. Inclusion Modification
5. Conclusion

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 Steel cleanliness is the one unifying theme in all steel
plants as problems in steel cleanliness can lead to
internal rejects or customer dissatisfaction with steel
products. Thus all steel plants are continually
attempting to improve their practices to produce more
consistent products.

Two main keys to the production of quality steel products

Chemistry and Inclusion control

These results can only be reached by a strict control of process

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 Non-Metallic Inclusion: Non-metallic inclusions are
chemical compounds of metals (Fe, Mn, Al, Si, Ca)
with non-metals (O, S, C, H, N). Non-metallic
inclusions form separate phases.

Clean Steel: Clean Steel refers to steel which is

free from inclusions and Level of cleanliness of
steel is determined by no. of inclusions per ton of
steel.

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The study of non-metallic inclusion is important for two
reason
1) The first is their influence on the properties and the
quality of steel products. This is a significant aspect
from the point of view of steel product users, who have
to take into account the presence of inclusions in
evaluating the material behaviour in working condition.

2) The second reason is that the study of inclusion allows

to estimate techniques and chemical reactions in steel
refining.

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Despite of small content of non-metallic inclusions in
steel (0.01-0.02%) they exert significant effect on the
steel properties such as:
- Tensile strength
- Deformability (ductility)
- Toughness
- Fatigue strength
- corrosion resistance
- Weldability
- Polishability
- Machinability
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 Non metallic elements
Internal
Hydrogen soundness
Electromagnetic Carbon Deep drawing
properties
Nitrogen
Surface defects
Toughness
Oxygen
Fatigue
Weldability Phosphorus
Anisotropy
Sulfur
Bending
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 Oxides: FeO, Al2O3, SiO2, MnO, Cr2O3 etc.
Sulfides: FeS, MnS, CaS, MgS, Ce2S3 etc.
Oxysulfides: MnS*MnO, Al2O3*CaS, FeS*FeO etc.
Carbides: Fe3C, WC, Cr3C2, Mn3C, Fe3W3C etc.
Nitrides: TiN, AlN, VN, BN etc.
Carbonitrides: Titanium carbonitrides, vanadium
carbonitrides, niobium carbonitrides etc.
Phosphides: Fe3P, Fe2P, Mn5P2

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 Micro Inclusion: 1-100 m m
Beneficial as they restrict grain growth, increase yield
strength and hardness
Act as a nuclei for precipitation of carbides and nitrides

Macro Inclusion : >100 m m

Harmful in nature so must be removed

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 Product Allowed impurities Allowed size (mm)
(in ppm)
Automotive Sheet & C<30, N<30, TO<20 100
Deep drawing sheet
Drawn and Ironed C<30, N<40,TO<20 20
Cans
Tire Cord H<2, N<40, TO<15 10
Ball Bearings [Ti] < 15, TO<10 15
Line pipe S<10, N<50, TO<30 100
Wires N<40, TO<15 20
Heavy plate H<2, N<40, TO<20 13

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 Globular shape
Platelet shaped
Dendrite shaped
Polyhedral Shaped

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SEM image of an inclusion observed in
the duplex stainless steel after calcium
treatment 12
(A): inclusion containing Si and Cr. (B): inclusion containing Al and Cr.
Formation Mechanism of Non-Metallic Inclusions in Stainless Steel13
a) As-polished (2-dimensional) steel sample showing Al2O3 dendrite
b) steel sample showing the same Al2O3 dendrite(SEM image)

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 Thermal Expansion:

MnS, CaS etc. have a thermal expansion greater than

steel matrix.
- On heating steel, void or parting of the matrix can
occur. The void act as crack

Al2O3, SiO2, CaO.Al2O3 etc have a thermal expansion

smaller than steel matrix
- On heating internal stresses developed

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 Density & Melting Point:
Compound of Melting Point(oC) Density at 20oC
Inclusion (g/cm3)
FeO 1369 5.8
MnO 1785 5.5
SiO2 1710 2.2-2.6
Al2O3 2050 4.0
CrO2 2280 5.0
TiO2 1825 4.2
ZrO2 2700 5.75
(FeO)2.SiO2 1205 4.35
FeS 988 4.6
MnS 1620 4.04
MgO 2800 3.58 16
 Plastic Deformability:
Calcium aluminates and Al2O3 inclusions in steel are un-
deformable at temperatures of interest in steelmaking
Spinel type double oxide AOB2O3 are deformable at
temperature greater than 1200oC
(where A is Ca,Fe(l),Mg, Mn & B is Al, Cr )
Silicate are deformable at higher temperature.
FeO, MnO are plastic at room temp but gradually lose
plasticity above 400oC
Mns is highly deformable at 1000oC but slightly less
deformable above 1000oC
Pure silica is not deformable upto 1300oC

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 Inclusion counts are performed to assess their
shape, quality and distribution to assess about the
cleanliness of steel
Inclusion Analysis
Sample preparation

Qualitative Assessment Quantitative Assessment

Dissolution of matrix by
SPEED method
Inclusion species and
morphology study by
SEM and EDS
Image acquisition by SEM
Back scattered electron mode
Inclusion counting by
image analysis
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Images acquired using (a) optical microscopy, (b) laser confocal microscopy,
(c) SEM (secondary electron mode) and (d) SEM (backscattered electron mode) 19
Glassy Al2O3 (globular) inclusions Glassy Al2O3 (plate) inclusions
found in 1018S furnace tap sample found in 1018S ladle sample 20
Oxide inclusions found in ladle Oxide inclusion found in billet
sample: alumina sample: alumina dendrites
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Oxide inclusions found in A529 ladle sample: a) alumina and galaxite (G)
b) alumina cluster
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 Mechanism of inclusion formation:

Indigenous inclusions are formed in liquid, solidified

or solid steel as a result of chemical reactions
(deoxidation, desulfurization) between the elements
dissolved in steel.

Exogenous inclusions are derived from external

sources such as furnace refractories, ladle lining, mold
materials etc.

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 Source of Inclusion:

I. Primary inclusions: generated during deoxidation

reaction
II. Secondary inclusions: generated due to equilibrium
shift as temperature decreases during vessel
transfer, such as tapping and teeming operations
III. Tertiary inclusions: generated during the process of
solidification, usually characterized by rapid cooling
IV. Quaternary inclusions: generated during solid state
phase transformation, which causes changes in
solubility limits of various constituents
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There are three stages of inclusions formation:
1. Nucleation
Nuclei formed as a result of super-saturation of the solution with
the solutes
The nucleation process is determined by surface tension on the
boundary inclusion-liquid steel.
The nucleation process is much easier in the presence of other
phase (other inclusions) in the melt.
2. Growth
Growth of a separate inclusion continues until the chemical
equilibrium is achieved (no super-saturation).
very slow process
3. Coalescence and agglomeration
Motion of the molten steel due to thermal convection or forced
stirring causes collisions of the inclusions, which may result in
their coalescence (merging of liquid inclusions) or agglomeration
(merging of solid inclusions)
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 Besides of the shape of non-metallic inclusions their
distribution throughout the steel grain structure is very
important factor determining mechanical properties of the
steel.
Homogeneous distribution of small inclusions is the most
desirable type of distribution.
Location of inclusions along the grain boundaries is
undesirable since this type of distribution weakens the metal.
Clusters of inclusions are also unfavorable since they may
result in local drop of mechanical properties such as toughness
and fatigue strength.

Distribution of non-metallic inclusions may change as a result

of metal forming (eg. Rolling).
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Al2O3 (inclusion in steel) SEM image

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 Inclusion can be controlled at:
a) During liquid steel processing stage
b) During solid state processing

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i) Control of inclusion during tapping of steel
Carry-over slag to be minimized

- Carry over of 1 kg FeO in slag decrease Al by 0.286 kg ,

which in turn forms 0.51 kgAl2O3
- No. of inclusion are 240 per kg of carry over FeO of slag

ii) Control of inclusion during treatment of steel

Stirring of steel bath accelerate the inclusion float to
surface

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iii) Control of inclusion during teeming of steel
Shrouding of molten steel stream in order to avoid re-
oxidation.
Proper selection of tundish flux
Segregation during solidification to be avoided

iv) Control of inclusion during Solid state processing

Working temp range 800-1200oC
Inert atmosphere to avoid oxidation

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 Depends on application, Inclusion Modification
Technique is based on design of inclusions so as
to minimize their harmful effects on the product
properties.

Uniformly dispersion of inclusion in the matrix

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 It should have high chemical affinity for the
inclusion
It should be able to modify the composition so that
it becomes liquid.
It should be able to modify the shape i.e sharp
edges and corner of inclusion to spherical.

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 Mainly Al2O3 and MnS inclusions are modified

Al2O3 inclusions are solid at casting temperature & brittle in nature.

Therefore clog the nozzle at continuous casting and breaks on
deformation

MnS inclusion in steel on deformation becomes stringer type.

Ca is used widely to modify inclusion

Solubility of C in steel is 320 ppm at 1600oC
Density of Ca: 1.55 g/cm3
Melting Temp of Ca: 1439oC
Form vapour at steel temperature 1600oC

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 CaO-Al2O3 Equilibrium Phase diagram

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Compound Melting Temp (oC) Ca/Al
Al2O3 2050 --
CaO.2 Al2O3 1727 0.37
CaO. Al2O3 1595 0.74
12CaO.7Al2O3 1400 1.27
3CaO.Al2O3 1527 2.22
CaS 2000 --
MnS 1620 --

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 Ca first modify the oxide inclusion
Thermodynamically it is easier to form CaO.2Al2O3
Then converted to CaO.Al2O3 and finally liquid calcium
aluminate rich in CaO
Then Ca desulphurise to very low levels.
When Ca content reach a certain level (~34ppm), CaS
precipitation begins
This will result in precipitation of CaS which forms a
duplex inclusion in which CaS-MnS ring surrounds
calcium aluminate core. This type of inclusion is
spherical and does not elongate.

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 Ca treatment is commonly used to control the shape and
composition of both oxydes and sulphides inclusion in Al-Killed
steel. The Ca additions reacts with solid Al2O3 inclusion.
Generally Ca. aluminates of lower melting points. Some of the Ca
may also react with dissolved sulpher resulting in the formation of
Ca or Ca-Mn sulphide inclusion. Problem of nozzle clogging are
often related to micro-inclusion composite either aluminate with
a high Al2O3 or CaS inclusion are solid at steel melting
temperature promoting nozzle blockage.

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 During Ca treatment of Al-killed steel, some Ca dissolved in the
steel and subsequently react with solid AL2O3 inclusion to form
calcium silicate. As the addition of Ca proceeds, the inclusion
become increasing rich in CaO and their liquidus temperature
decreases. Some of the added calcium may combined with sulpher
to produce Ca-Mn sulphide.
When Ca content reached a certen level ~ 34 ppm, CaS
precipitation begins

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Oxide inclusions found in ladle tap sample: calcium aluminate
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 It not always important to remove the inclusion from
steel, however , the bigger size inclusion are to be
removed.
Smaller size inclusion is not all the time required that
can be removed, however, if those inclusions can be
modified in terms of their melting point, or in terms of
their sharp edges or corner edges modified to spherical
globule, then it will be good. From application point of
view , they will not have a harmful effect.

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