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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

Introduction
1. Introduction
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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1 Definition
1.1 Definition
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.

1 Reason of study of inclusion


1.1 Reason of study of inclusion
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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Influence of Inclusion on Steel Properties


1.2 Influence of Inclusion on Steel Properties
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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Influence of Inclusion on Steel Properties


1.2 Influence of Inclusion on Steel Properties
Non metallic elements
Internal
Hydrogen
soundnes
sDeep
Carbon
Electromagn
etic
properties
Toughne
ss
Weldability

drawing

Nitroge
n
Oxygen

Surface
defects

Phospho
rus

Anisotropy

Sulfur

Fatigue

Bending
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3 Type of Inclusion
1.3 Type of Inclusion
Oxides: FeO, Al2O3, SiO2, MnO,

Cr2O3etc.
Sulfides: FeS, MnS, CaS, MgS,

Ce2S3etc.
Oxysulfides: MnS*MnO, Al2O3*CaS,

FeS*FeO etc.
Carbides: Fe3C, WC, Cr3C2, Mn3C,
Fe3W3C etc.
Nitrides: TiN, AlN, VN, BN etc.

4 Size of Inclusion
1.4 Size of Inclusion
Micro Inclusion: 1-100 m
Beneficial as they restrict grain growth, increase yield
strength and hardness
Act as a nuclei for precipitation of carbides and nitrides
MacroInclusion:>100 m
Harmful in nature so must be removed

Requirements for Clean Steels


1.4 Requirements for Clean Steels
Allowed impurities
(in ppm)
C<30, N<30, TO<20

Allowed size (m)

Drawn and Ironed


Cans

C<30, N<40,TO<20

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Tire Cord

H<2, N<40, TO<15

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[Ti] < 15, TO<10

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S<10, N<50, TO<30

100

N<40, TO<15

20

H<2, N<40, TO<20

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Product
Automotive Sheet &
Deep drawing sheet

Ball Bearings
Line pipe
Wires
Heavy plate

100

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5 Morphology of Inclusion
1.5 Morphology of Inclusion
Globular shape
Platelet shaped
Dendrite shaped
Polyhedral Shaped

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5 Morphology of Inclusion
1.5 Morphology of Inclusion

SEM image of an inclusion


observed in the duplex
stainless steel after calcium

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5 Morphology of Inclusion
1.5 Morphology of Inclusion

(A): inclusion containing Si and Cr. (B): inclusion


containing
and Cr.
FormationAlMechanism
of Non-Metallic Inclusions

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5 Morphology of Inclusion
1.5 Morphology of Inclusion

a) As-polished (2-dimensional) steel sample showing


Al2O3 dendrite
b) steel sample showing the same Al2O3 dendrite(SEM
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image)

6 Properties of Inclusion
1.6 Properties of Inclusion
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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6 Properties of Inclusion
1.6 Properties of Inclusion
Density & Melting Point:
Compound of
Inclusion
FeO
MnO
SiO2

Melting Point(oC)
1369
1785
1710

Density at 20oC
(g/cm3)
5.8
5.5
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
MnS
MgO

988
1620
2800

4.6
4.04
3.58

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6 Properties of Inclusion
1.6 Properties of Inclusion
Plastic Deformability:
Calcium aluminates and Al2O3 inclusions in steel are undeformable 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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0 Inclusion Assessment
2.0 Inclusion Assessment
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

Image acquisition by
SEM
scattered
Back
Inclusion
electron
counting mode
by
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image analysis

0 Inclusion Assessment
2.0 Inclusion Assessment

Images acquired using (a) optical microscopy, (b) laser


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confocal microscopy,

0 Inclusion Assessment
2.0 Inclusion Assessment

Glassy Al2O3 (globular)


inclusions found in 1018S

Glassy Al2O3 (plate)


inclusions found in

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0 Inclusion Assessment
2.0 Inclusion Assessment

Oxide inclusions found in


ladle sample: alumina

Oxide inclusion found in


billet sample: alumina
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dendrites

0 Inclusion Assessment
2.0 Inclusion Assessment

Oxide inclusions found in A529 ladle sample: a)


alumina and galaxite (G)

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0 Source of Inclusion Formation


3.0 Source of Inclusion Formation
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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1 Inclusion Source & Control


3.1 Inclusion Source & Control
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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2 Inclusion Formation
3.2 Inclusion Formation
There are three stages of inclusions formation:
1. Nucleation
Nucleiformedasaresultofsuper-saturationofthesolutionwiththesolutes
Thenucleationprocessisdeterminedbysurfacetensionontheboundary
inclusion-liquidsteel.
Thenucleationprocessismucheasierinthepresenceofotherphase(other
inclusions)inthemelt.
2. Growth
Growthofaseparateinclusioncontinuesuntilthechemicalequilibriumis
achieved(nosuper-saturation).
veryslowprocess
3. Coalescence and agglomeration
Motionofthemoltensteelduetothermalconvectionorforcedstirring
causescollisionsoftheinclusions,whichmayresultintheir
coalescence(mergingofliquidinclusions)oragglomeration(mergingof
solidinclusions)
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3 Distribution of Inclusion
3.3 Distribution of Inclusion
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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3 Distribution of Inclusion
3.3 Distribution of Inclusion

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3 Distribution of Inclusion
3.3 Distribution of Inclusion

Al2O3 (inclusion in steel) SEM


image

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

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4 Control of Inclusion
3.4 Control of Inclusion
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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4 Control of Inclusion
3.4 Control of Inclusion
iii) Control of inclusion during teeming of steel
Shrouding of molten steel stream in order to avoid reoxidation.
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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0 Inclusion Modification
4.0 Inclusion Modification
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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Requirement for Inclusion Modification


4.1 Requirement for Inclusion Modification
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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Ca-treatment for inclusion modification


4.2 Ca-treatment for inclusion modification

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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Ca-treatment for inclusion modification


4.2 Ca-treatment for inclusion modification

CaO-Al2O3 Equilibrium Phase diagram

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Ca-treatment for inclusion modification


4.2 Ca-treatment for inclusion modification
Compound

Ca/Al

Al2O3
CaO.2 Al2O3

Melting Temp
(oC)
2050
1727

CaO. Al2O3

1595

0.74

12CaO.7Al2O3 1400

1.27

3CaO.Al2O3

1527

2.22

CaS
MnS

2000
1620

---

-0.37

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Ca-treatment for inclusion modification


4.2 Ca-treatment for inclusion modification

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Ca-treatment for inclusion modification


4.2 Ca-treatment for inclusion modification

Ca first modify the oxide inclusion

Thermodynamically it is easier to form CaO.2Al 2O3 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 for inclusion modification


4.2 Ca-treatment for inclusion modification
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 microinclusion composite either aluminate with a
high Al2O3 or CaS inclusion are solid at steel
melting temperature promoting nozzle
blockage.
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Ca-treatment for inclusion modification


4.2 Ca-treatment for inclusion modification
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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Ca-treatment for inclusion modification


4.2 Ca-treatment for inclusion modification

Oxide inclusions found in ladle tap sample:


calcium aluminate

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Conclusion
5. Conclusion
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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THANK YOU

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