Prepared by

Monir Hamed
Feb. 2012

Clean steel
1. What is clean steel?
Clean steel refers to steel free from inclusions but practically, it is not possible to produce
steel without any inclusions.

2. Characteristics of clean steel:

Low total oxygen content
Low level of non-metallic inclusions (<50)
No existence of macro inclusions (>50)
Inclusion morphology (spherical)
Low solute elements: O, N, P, S & H
Low residual elements: Cu, Pb, Zn ,etc

3. Types of inclusions:
Oxides:
-FeO ,SiO2 ,Al2O3 ,etc or complex oxides.

Sulphides
-FeS, MnS, MgS, etc or compounds

Nitrides
-TiN, AlN, ZrN, etc or compounds

Phosohides
-Fe3P, Mn5P2, etc

4. Disadvantages of high level of NMI & Macro Inclusions:

They deteriorate the following properties:

Impact strength

Fatigue strength

Formability

Drawability

Weldability especially (ERW)

Corrosion resistance

Resistance to HIC (hydrogen induced cracking)

5. Cleanliness Requirements for Various Steel Grades:

Application

Key Property

Critical Inclusion
Size,m

Deep drawing
Cans sheets

-Flange cracking

20

Automotive
and deep
drawing sheets

-Rupture
-Cracking

50

Sour gas pipes

-HIC

Line pipes

-SCC

Bearing

-Fatigue
cracking

Tire cord

-Rupture

Spring wire

-Fatigue
cracking

IF Steel

-Rupture
-Cracking

Shape control

Shape control
100

Maximum Allowed Impurity

content ,ppm
C 30
N 40
T.O 20
C 30
N 30
S
P
H

10
50
1.5

S 30
N 50
T.O 30
H 1.5

15

T.O 10
Ti<15(TiO2,TiN:non-deformable)

10
Shape control

H 2
N 40
T.O 15

Shape control
Shape control

T.O 20
C 30
N 40
T.O 40

6. Properties of Inclusions:
6.1

Thermal expansion
Inclusions like MnS ,CaS have thermal expansion greater than steel matrix.
On heating steel voids can occur and act as cracks.
Inclusions like Al2O3, SiO2 & CaO.Al2O3 have thermal expansion smaller than steel
matrix.
On heating steel internal stresses can occur.

6.2

Density & Melting Point

Inclusion

Melting point Density at 200C,gm/cm3

FeO

1369

5.8

MnO

1785

5.5

SiO2

1710

2.4

Al2O3

2050

4.0

Cr2O3

2280

5.0

TiO2

1825

4.2

ZrO2

2700

5.75

(FeO)2SiO2

1205

4.35

FeS

988

4.6

MnS

1620

4.04

MgO

2800

----

12CaO.7Al2O3*

1400

----

Inclusions like Al2O3, TiO2, MgO are solids during steelmaking process.

6.3

Plastic deformability
The plastic deformability of an inclusion will govern any change in its shape under
the action of external forces and will determine the amplitude of stress concentration.
Brittle inclusion are dangerous as they may crack and cause fracture.

CaO.Al2O3 and Al2O3 are undeformable at temperature of interest in

steelmaking

Spinal type oxides AOB2O3 are deformable at temperature > 12000C where
A: Ca, Fe, Mg, Mn
B: Al, Cr

FeO, MnO are plastic at room temperature but lose plasticity above 4000C.

MnS is highly deformable at 10000C but slightly less deformable above

10000C

Pure SiO2 is not deformable up to 13000C.

7. Sources of Non Metallic & Macro inclusions:

Sources of Inclusions

Endogenous
Inclusions
Deoxidation products

Exogenous inclusions

Reoxidation

Reaction of soluble oxygen &

deoxidizers Al & Si

Reaction between Asol &

FeO, MnO , SiO2

Inclusions from refractories

or linning
Slag & linning
reactions

Failure of weir
or dam
Exposure to atmosphere
(poor sealing)
Erosion during
casting
Reoxidation can cause
nozzle clogging

Slag entrapment

Too high argon

stirring rate

Filling TD in the
presence of slag

Low bath depth in

tundish (vortex
formation)
High mold level
fluctuation

NB
Some grades are corrosive (high Mn &high soluble O2)

It is not recommended too much flow

towards top surface or stagnant surface

8. Characteristics of exogenous inclusions:

Large size
Multiphase
Irregular shape
Small number
Often found near the surface
More harmful to steel properties

9. Clean steel practice:

Minimize slag carryover from EAF at tapping (hot heel: ~ 30 ton)
Slag treatment to reduce FeO + MnO

(FeO + MnO < 1%)

Ca treatment at high feeding speed

Minimum 7 minutes rinsing with low argon flow rate after Ca-treatment
Control mold level within 3mm
Control tundish super heat to be 10 ~ 250C
NB
Too low super heat doesnt allow for large inclusions to float

Ca-treatment
Purpose
To modify inclusion shapes to avoid alumina (Al2O3) build up on the
internal

surface

of

the

submerged

entry nozzle

(SEN) causing

clogging.Al2O3 is very detrimental to machinability

Steel desulfurization
Steel deoxidation
Ca treatment pattern
Al must be adjusted before Ca-treatment
Ca-treatment according to the type of Ca-wire used
Keeping 10 ~ 15 minutes soft bubbling between last Al addition and Catreatment start
minutes soft bubbling for inclusion floating after Ca injection
Aim of Alsol/Ca (it is recomnded to be < 15%)
NB
Check slag surface before Ca injection and use pipe to open a hole in
case of hard slag surface
Use suitable Ca-wire in case of galvanized steel & non galvanized steel
After Ca injection, sample is taken after 2 minutes soft bubbling
Ca-wire speed is > 150m/min
Reactions
[Ca] + [O] = (CaO)

(1)

[Ca] + [S] = (CaS)

(2)

(Al2O3) +3(CaS) = 3(CaO) + 2[Al] + 3[S]

[S] + (CaO) = (CaS) + [O]
2[Al] + 3[O] = (Al2O3)

(3)

(4)
(5)

[Ca] + (X+(1/3))(Al2O3) = (2/3) [Al]

(6)

Calcium aluminates retained in liquid suppress the formation of MnS stringers

during solidification of steel. The modification of shape of inclusions and the low
melting point of these inclusions have the following advantages:
Improve steel castability (minimize nozzle clogging).
Minimize susceptibility steel to heat-affected zone cracking.
Minimize susceptibility of HSLA steels to HIC in sour gas/oil environment.
Increase impact energy

Binary diagram of CaO & Al2O3

The morphology of Al2O3 is dendritic and it does not float easily so Ca is added to
turn the dendritic morphology into spherical one to facilitate its floating to the slag
layer.

Modification of inclusions by Ca treatment