Unit-III
Inclusions in steels
Clean Steel
• Clean steel refers to steel which is free from inclusions. Inclusions are
nonmetallic particles embedded in the steel matrix. Practically it is not
possible to produce steel with out inclusions. Therefore a cleaner steel
can be produced i.e. one containing much lower level of harmful macro
inclusions.
• Source of Inclusions:
• Inclusion can form either (a) during transfer of molten steel from one
reactor to other or (b) during solidification of steel.
• (a) (i) Inclusion may form during tapping of molten stream from
BOF/EAF to ladle.
(ii) oxygen pickup by teeming stream; air entrapment in
molten steel stream brings oxygen and FeO formation is initiated.
(iii) Treatment of steel in ladle; deoxidation and synthetic slag
treatment, oxide/sulphide inclusions may form.
• (b) (i) Reaction between rejected solute elements during
solidification Ex: reaction between S and Mn and between
O2 and Al etc.
(ii) Mechanical and chemical erosion of refractory.
• Types of inclusions:
Inclusions are chemical compounds of metals like (Fe, Mn, Al, Si, Ca)
with non metals (O, S, N, C, H).
Oxides: FeO, Al2O3, SiO2, MnO, Al2O3.SiO2,
Sulphides: FeS, CaS, MnS, MgS
Nitrides: TiN, AlN, VN etc.
Oxysulphides: MnS. MnO, Al2O3. CaS etc.
Phosphides: Fe3P, Fe2P, Mn5P2.
• Morphology:
• The non metallic inclusions are having different shapes.
• Globular shape: This shape is more desired since their effect on the
mechanical properties of steel is moderate.
• Platelet shape: Steels deoxidized by Al contain MnS and oxy-
sulphides in form of thin films ( platelets) located along the grain
boundaries. Such inclusions are formed as a result of eutectic
transformation during solidification (L S + S).
• These inclusions are not desirable because they weaken the grain
boundaries and cause adverse effects on the mechanical properties,
particularly hot shortness.
• Dendrite shape inclusions: Excess amount of strong deoxidizer (Al,
Mn) results in formation of dendrite shape oxide and sulphide
inclusions. These inclusions have melting points higher than that of
steel. Sharp edges and corners of the dendrite shaped inclusions may
cause local concentration of internal stress, which decreases ductility,
toughness and fatigue strength of the steel.
• Polyhedral inclusions: Morphology of dendrite shape inclusions may
be improved by addition of small amount of rare earth (cerium,
lanthanum). Since their shape nearing the globular shape, polyhedral
inclusions cause less effect on properties of steel compared to dendrite
shape.
(a) small spherical inclusions,
(b) octahedral inclusions,
(c) small polyhedral inclusions,
(d) large polyhedral inclusions,
(e) plate-like inclusions,
(f) dendrite
(g) cluster, and
(h) aggregate.
• Size of inclusions:
• There are micro inclusions (size 1-100µm) and macro inclusions
(size > 100µm). Macro inclusions are harmful.
• Micro inclusions are beneficial as they restrict grain growth,
increase yield strength and hardness.
• Distribution of non metallic inclusions:
• In addition to size and shape of the nonmetallic inclusions, the
distribution through out the steel grain structure is very important
factor determining mechanical properties of the steel.
• There are three types of distribution patterns of nonmetallic
inclusion.
– Homogeneous distribution of small inclusions is the most
desirable type of distribution. In some steels carbides or nitrides
homogeneously distributed in the steel and these increases strength of steel.
• Location of inclusions along the grain boundaries of the steel is
undesirable since this type of distribution weakens the structure of the
steel.
• Clusters of inclusions is the third type of distribution and this type is
also unfavorable since it may result into deterioration of mechanical
properties such as toughness and fatigue strength etc.
• Distribution of nonmetallic inclusions may change as a result of
working of steel (rolling, forging etc.).
• Ductile inclusions are deformed and elongated in the direction of
working. The less ductile inclusions break during working and forms
chains of fragments.
• Elongated inclusions and fragmented chain of inclusions result
anisotropy of mechanical properties.
• Mechanical properties in transverse direction are lower than those
parallel to the direction of working.
• Properties of inclusions:
(1) Thermal expansion:
• There are inclusions like MnS, CaS etc. which have thermal expansion
greater than steel matrix. On heating steel with these types of inclusions
parting of the matrix can occur. This parting or void can acts as crack.
• On the other hand Al2O3, SiO2 and CaO.Al2O3 etc. inclusions have
thermal expansion smaller than steel matrix. On heating steels with these
type of inclusions internal stresses of thermal origin can develop.
(2) Density and Melting point:
S.No. Composition Melting point Density at 20℃ . g/cm3
1. FeO 1369 5.8
2. MnO 1785 5.5
3. SiO2 1710 2.2-2.6
4. Al2O3 2050 4.0
5. TiO2 1825 4.2
6. MnS 1620 4.04
7. MgO 2800 3.58
(3) Plastic deformability:
• Brittle inclusions are dangerous as they may crack and cause
fracture of the component under the application of external force.
• Al2O3 inclusions in steel are undeformable at temperature of interest
in steel making.
• Double oxides like CaO. Al2O3, FeO. Al2O3, MgO. Al2O3 etc. are
deformable at temperatures greater than 1200℃.
• FeO, MnO are plastic at room temperature but gradually lose
plasticity above 400℃.
• MnS which is highly deformable at 1000 ℃ temperature but
becomes slightly less deformable above 1000℃.
• Control of inclusions:
• Inclusions can be controlled either at
– During liquid steel processing stage.
– During solid state processing.
• Liquid state processing:
• During liquid state processing inclusion control can be exercised at
tapping and teeming of steel.
• During tapping of molten steel from BOF/EAF carry over slag must be
minimized if not prevented.
• BOF slags are highly basic in nature and contains oxides like FeO,
MnO, SiO2, CaO, MgO etc. These oxides reacts with Al during ladle
treatment and lead to inclusion formation.
3FeO + 2 Al = Al2O3 + 3Fe
3MnO + 2Al = Al2O3 + 3Mn
• Carryover of 1kg FeO in slag decreases Al by 0.286 Kg. which in turn
forms 0.5 kg Al2O3.
• Another way for inclusion formation is reoxidation of tapping stream.
Tapping stream exposes very large surface area in the atmospheric and
hence oxygen pickup leads to oxide inclusion formation.
• Molten steel stream after treatment in the ladle is teemed into tundish
and then from tundish to mould in the continuous casting.
• Teeming of steel from ladle to tundish requires shrouding of molten steel
stream in order to avoid reoxidation. Here macro-inclusion rich in FeO
and MnO can form. Use of shrouded and submerged nozzles will help
control inclusion formation.
• Teeming of molten steel from tundish to continuous casting mould needs
extra precaution. Inclusions do not get sufficient time for separation
owing to faster solidification in mould.
• Teeming stream through the nozzle submerged in molten stream are the
effective means to avoid inclusion formation.
• Selection of tundish flux:
• Tundish flux should be selected such that it can easily absorb inclusions
floating in the tundish. At the same time flux should also cover molten
steel to prevent oxidation.
• Inclusion can also form in the mold during solidification. As the steel
solidifies the excess solute elements like oxygen, Sulphur, manganese
etc. are rejected and lead to inclusion formation.
• Solid state processing:
• In the solid state processing steel is heated to a temperature ranging
between 800-1200℃ to perform heat treatment and hot working. Here
steel must be heated under inert atmosphere to avoid oxidation.
• During welding, liquid pool is in contact with air and steel is prone to
oxidation. Inert shielding may avoid the inclusion formation.
• Inclusion Engineering ( Modification):
• Inclusion engineering refers to modifying the inclusion either in
terms of chemical composition or shape , so that harmful effects of
the inclusions can be converted to improve the steel properties.
• Inclusion engineering also involves distribution of inclusion
uniformly in the matrix.
• Requirements for inclusion engineering:
• One of the main requirement is to find a element which should be
added to modify the inclusion. Element should have following
properties:
– It should have high chemical affinity for the inclusion.
– It should be able to modify the composition so that it becomes
liquid.
– It should also be able to modify the shape i.e. sharp edges and
corner of inclusion to spherical.
• Mainly Al2O3 and MnS inclusions are modified. Al2O3 inclusions
are brittle and breaks on deformation. Similarly MnS inclusion in
steel on deformation becomes stringer type.
• In Al killed steels, Al2O3 inclusions are formed. Al2O3 (M.P.
2072℃) inclusions are solid at steel making temperature and brittle
in nature.
• During continuous casting, Al2O3 inclusions clog the nozzle and
consequently steel flow rate to the mold is affected.
• Calcium is introduced into molten steel as Ca-Si based alloy powder
either by powder injection deep into molten bath or another method
is wire feeding at a speed of 80-300 m/min.
• Ca treatment at the final stage in a ladle or tundish was found to
eliminate clogging the nozzle because the deoxidation product is a
liquid consisting of CaO-Al2O3.
• CaO-Al2O3 Equilibrium Phase diagram
17
S.No. Compounds Melting point (℃) Ca/Al
1. 3CaO.Al2O3 1527 2.22
2. 12CaO.7Al2O3 1400 1.27
3. CaO.Al2O3 1595 0.74
4. CaO.2Al2O3 1727 0.37
• Oxide shape control:
• For a normal Al killed steel Ca will first modify the oxide inclusions.
Thermodynamically it is easier to form CaO. 2Al2O3 type of
inclusion which will be converted to CaO. Al2O3 and finally liquid
calcium aluminate rich in CaO. The Ca will then desulphurize steel
to very low levels.
• From the above table, it is observed that 12CaO.7Al2O3 has low
melting point and will remain in the liquid at steel making
temperatures. Also, the Ca/Al ratio is 1.27. This suggest that Ca/Al
ratio has to be adjusted at 1.27 in order to obtain liquid product.
Oxide inclusions found in ladle tap sample: calcium aluminate
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• Sulphide shape control:
• MnS elongates in the direction of rolling and becomes stringer type
inclusions. Stringer type inclusions should be modified if not
eliminated.
• For sulphide shape control, it is necessary to desulphurize steel to
very low value say 0.006%.
• Addition of Ca to Al killed steel will first form calcium aluminate
inclusion. If Ca content reaches a certain level (~ 34 ppm), CaS
precipitation begins, which forms a duplex inclusion in which a
CaS-MnS ring surrounds calcium aluminate core. This type of
inclusion is spherical and doesnot elongate.
• Effect of rare earth elements:
• When rare earth elements like cerium are added to steel they can
react to form an oxide, sulphide or oxysulphides.
2Ce + 3O = Ce2O3
Ce + S = CeS
2Ce + 2O+ S = Ce2O2S
• It must be noted that rare earths have high atomic wt. and their
oxides, sulphides and oxysulphides have density 5-6 g/cm3 as
compared with other oxides.
• These inclusions do not float easily
• Rare earth are strong deoxidizers and desulphurizer as well.
• Inclusion Assessment:
• Nonmetallic inclusions in steel are characterized by the size, shape,
concentration and distribution.
• The routine plant procedure employs the microscopic method. From
the shape of the inclusion and knowledge of the steel making
process in a plant, it is inferred to whether it is silica/silicate,
aluminate or sulphide inclusion.
• EPMA enables to determine the chemical composition of individual
inclusion.
• Quantimet (equipment) has an optical microscope fitted with video
screen. It can scan the specimen very quickly and provide a variety
of information such as inclusion size, distribution, number, volume
fraction etc.
Images acquired using (a) optical microscopy, (b) laser confocal microscopy,
(c) SEM (secondary electron mode) and (d) SEM (backscattered electron mode)
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Glassy Al2O3 (globular) inclusions found in Glassy Al2O3 (plate) inclusions found in
1018S furnace tap sample 1018S ladle sample
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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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• According to the shape and distribution inclusion are classified in to 5
groups:
• Group A (sulphide type):- They are individual grey particles with a wide
range of aspect ratio (length/ width) and have generally rounded end.
• Group B (aluminate type):- These inclusions are non-deformable, low
aspect ratio (less than 3), black or bluish particles, atleast 3 aligned in the
deformation direction.
• Group C (silicate type):- These are highly malleable, black or dark grey
particles with aspect ratio equal to 3 and generally have sharp ends.
• Group D (globular oxide):- These are non-deformable, circular, L/W< 3,
black or bluish, randomly distributed particles.
• Group DS (single globular type):- circular, single particle with dia≥
13𝜇𝑚.
COMPARISON CHART- A (Sulfide type)
COMPARISON CHART- B (Aluminate type)
COMPARISON CHART- C (Silicate type)
COMPARISON CHART- D (Globular type oxides)
