Impact of Refractories Corrosion On Industrial Processes: 4.1. Steel Making

FIRE COURSE Unitecr2001, October 30th, 2011 Kyoto, Japan
4. Impact of refractories
corrosion on Industrial
processes
4.1. STEEL MAKING
J. Poirier
CNRS-CEMHTI, University of Orleans
FIRE COURSE Unitecr2001, October 30th, 2011 Kyoto, Japan
4. 1
STEEL MAKING - CONTENTS OF THE PRESENTATION
Introduction
Part I (4.1.1) : Flow control and interactions of refractories
and steel during continuous casting
o Protection between ladle and tundish
o Tundish lining
o Submerged nozzles
Part II (4.1.2) : Corrosion, cleanliness and steel quality

o Reactions between refractories, steel and slag
o Metallurgical consequences
Control of oxide cleanliness, Steel desulphuration, Ca treatments of
inclusions, Elaboration of ULC steels
Conclusion
INTRODUCTION
Surface micrograph showing fine particles at

grain boundaries
Steel-makers challenge
To propose steel grades with :
narrower composition ranges
lower guaranteed contents of residuals
controlled inclusion size distributions
To obtain
reproducible service
properties
TRIP 800
Introduction
Steel challenge Cleanliness /chemistry
Non metallic elements
Impact of refractories
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
In particular, steel cleanliness and purity requirements make

the selection of refractory products more and more important
Introduction
Steel challenge
Cleanliness /chemistry
Influence of non metallic elements on steel properties

Internal soundness
Hydrogen
Electromagnetic
properties
Carbon
Deep drawing
Nitrogen
Surface defects
Toughness
Oxygen
Control of inclusions
Weldability
Phosphorus
Weldability
Sulfur
Control of inclusions
Fatigue
Anisotropy
Bending
Introduction
Steel challenge
More and more complex elaboration to eliminate

non metallic elements
Vacuum treatment
Desulphuration treatment
C content < 15 ppm

is possible !
S content~ a few ppm
Element P
ppm
10
C
5
S
5
N
10
H
<1
O
5
Lower limits of residual elements in steel making elaboration

Introduction
Steel challenge
The impact of refractory products on the quality of the metal
3 aspects
1. The possibility to keep the chemical composition of

the liquid steel for a given process
Introduction
Steel challenge
2. The achievement of the required metal cleanliness :

the amount and the nature of non metallic inclusions
Introduction
Steel challenge
3. The prevention of defects concerning the steel surface

Introduction
Steel challenge
Main classes of refractories in relation

with the quality and metal cleanliness
Secondary metallurgy : for steel ladle
Fired and unfired bricks

Unshaped high alumina
or High alumina spinel
content products
Introduction
Steel challenge
Magnesia graphite
Magnesia chrome
Dolomite
High alumina, mainly bauxite products
Alumina - spinel

Secondary metallurgy : for degassing devices
RH/OB
Magnesia-chrome and alumina unshaped products

(containing or not spinel MgO-Al2O3)
Introduction
Steel challenge

Tundish lining and continuous casting
Steel ladle
Al2O3-C Stopper
Plate
Tundish
Al2O3 - C
Ladle Al2O3 - C
Shroud
Sprayed magnesia
Submerged
nozzle
Introduction
Steel challenge
Al2O3 - C and
ZrO2-C insert
Summary of different defect types in steel in relation

with the refractory products
Steel
Steel purity
- Carbon pick up
- Sulphide cleanliness
- N and H pick up
Inclusions and defects

- exogenous inclusions
- endogenous inclusions
TiN, Al2O3-MgO, MnOSiO2, Al2O3, SiO2
- splitting decohesion
(inclusions + gaz)
Longitudinal cracks
Heterogeneity of
solidification
Interactions
Pollution
Steel/slag/refractory
Materials and assembly

of refractories
Corrosion of slag line
Spalling
of wall
Erosion of
refractories
Reoxydation
Air leakage
Reactivity
Steel
refractory
Mastery of argon
injection
Al2O3
build up
Al2O3 clogging
Thermal transfert
Air leakage
PART 1. (4.1.1) FLOW CONTROL

INTERACTIONS OF REFRACTORIES AND STEEL
DURING CONTINUOUS CASTING
- Sliding gate system
-Protection between ladle and tundish
- Tundish lining
- Submerged nozzles
Sliding gate system

consists of a mechanical assembly containing the refractory plates
The basic function : the control of metal flow rate

Part 1. Continous casting
Sliding gate
Stopper
Tundish lining
Submerged nozzle
The plates of the sliding gate system

Subjected to severe thermo-mechanical stress
Lead to the cracking of the refractory in use
Al2O3 /SiC / C refractory
Cause of air leakage with effects on the cleanliness and the wear
Sliding gate
Stopper
Tundish lining
Submerged nozzle
Effect of the plate cracks on the nitrogen pick up

Shape of plates
2 points of
blockage
3 points of
blockage
Length of cracks
121 mm
76 mm
N pick up
1.96 ppm
0.58 ppm
Sliding gate
Stopper
Tundish lining
Submerged nozzle
Design of the plates of the sliding gate system
(a) cracks in a slide gate

air leakage
(b)
optimised design
no crack
In order to reduce cracking and to limit the re oxidation of the steel

Sliding gate
Stopper
Tundish lining
Submerged nozzle
The stopper
Al2O3/graphite products
The function : the control of metal flow rate

Sliding gate Stopper
Tundish lining
Submerged nozzle
The stopper
Injection of
argon
The stopper may be a

source of reoxidation
Air leakage due to :
an imperfect airtightness of
argon injection connection
the permeability of refractory
pieces
Tundish lining
Submerged nozzle
A argon injection system in the stopper in order

to limit air leakage
Graphite
compressed
joints
4
Air tightness
of quenouilles
the stopper
: measurement of
Etanchit
- Mesures chaud
leakage in use ( at high temperature)
3,5
Design to limit air

leakage
(l/mm)
Leakage
D fuite (l/min.)
Preheating
Prchauffage
of tundish
2,5
Coule
Casting
2
1,5
1
0,5
0
0
20
40
60
80
100
120
140
160
180
200
220
Temps (min.)
Time in mn
Tundish lining
Submerged nozzle
The tundish lining

Made of magnesia and forsterite (2MgO-SiO 2) monolithic
Tundish lining
Submerged nozzle
The tundish lining

The close contact between steel and the refractory lining allows a
pollution action ( exchange of oxigen, hydrogen, magnesium, silicium)
Preheating
Lining with
-a great porosity
- active surface
Lining after use

In use
Tundish lining
Submerged nozzle
Reduction of silica and iron oxydes present in refractories with

oxygen pick up in steel
3 (SiO2)refract. + 4 [Al]steel 3 [Si]steel + 2(Al2O3)
3 (FeO)refract. + 2 [Al]steel 3 [Fe]steel + 2(Al2O3)
Refractory
Steel
Quantity of oxygen (g)
Relationship between oxygen (caught by

aluminium) and the FeO content of the
tundish refractory (laboratory trials)
Preheating
at 180C
0,8
0,6
0,4
Preheating
at 1200C
0,2
0
% FeO
Lehmann and Al. 2nd Intern. Symp. On advances in refractories for the metallurgy industry, 1996
Tundish lining
Submerged nozzle
Transfer of magnesium and formation of MgO-Al2O3 spinels

Plant trials as well as the laboratory experiments demonstrate also a
chemical transformation of the forsterite into the MgO-Al 2O3 spinel
3(2MgO-SiO2) refr. + 4 [Al]steel 2(MgO-Al2O3)refr. + 4 (MgO)refr. +3 [Si]steel
% surfacique
de spinelle
%
spinel
25
20
15
10
5
0
40
Observation of spinel crystals

at the interface steel/refractory
laboratory trials
60
% MgO
80
100
du rfrac
The quantity of spinels is in relation to the

magnesia content in the refractory lining
Spalling of the MgO-SiO2 lining can lead to MgO-Al2O3 inclusions in steel

Tundish lining
Submerged nozzle
The tundish lining : hydrogen pick up
Hydrogen [ppm]
Diffusion of water from sray lining occurs and complete expulsion of the
moisture cannot be guaranted even when the tundish is well prea-heated
4
3,5
3
2,5
2
1,5
1
0,5
0
Hydrogen pick up at the

beginning of the casting
Number of casting during a sequence
Measurement of the hydrogen content in steel during a sequence of 3 ladles
To limit hydrogen pick up in the steel, it is important to improve the

refractory composition and the preheating procedures of the tundish
Part 1 Continous casting
Tundish lining
Submerged nozzle
Submerged nozzle materials

Al2O3/graphite products
One of the main problem : alumina
clogging for Al killed steels !
Clogging and unclogging lead

to metal contamination by
alumina particules or clusters
Alumina deposits
in a submerged nozzle
Tundish lining
Submerged nozzle
What caused clogging ?

Hydrodynamic factors :
metal flow velocities, turbulence zones associated with dead
zones, shape of submerged nozzles
Metallurgical factors:
steel grades, cleanliness and deoxidation
Thermal factors:
steel temperature, heterogeneous bath, insufficient
preaheating of nozzles
Interactions Al2O3-C refractories / steel and refractory
factors
choice and assembly of refractory materials
Tundish lining
Submerged nozzle
Morphology of deposits in submerged nozzles : 3 zones

A decarburized
zone
Refractory
3
On the hot face
plate like Al2O3 particles
Alumina particles + vitreous phase
Interactions Al2O3-C refractary/steel : deposit build up mechanism
Dissolution of the carbon of the Al2O3-C refractory into the steel

Build up of a first layer of deposit by volatilization and oxidation
reactions
Refractory
PO2 = 10-17 atm
Steel
PO2 = 10-11 atm
Mechanism of condensation
Tundish lining
Submerged nozzle
Dissolution of the carbon of the Al2O3-C refractory into the steel

Build up of a first layer of deposit by volatilization and oxidation
reactions
Alumina formation through oxidation of aluminium by
Carbon monoxide
CO (ref) [C]Fe + [O]Fe
CO(g) forms in the refractory
Aluminium oxidation
2[Al]Fe + [O]Fe Al2O3
Deposit
formation
Even if the steel is perfectly clean, the clogging
will
still occur !
Tundish lining
Submerged nozzle
Consequences
The alumina deposit increases with the content of oxide phases in the
Al2O3-C refractories (silica, alkalines) that are likely to be reduced by carbon
Alumina clogging does not occur
with high carbon content steel
Tundish lining
Submerged nozzle
Oxygen pick up and permeability of refractory products

Oxygen plays a fundamental role in the build up of deposits
in submerged nozzles
oxydation of dissolved Al in steel
condensation of the Na,K, Si, SiO gaz compounds into a
oxyde vitreous phase
Many sources of reoxydation
permeability of the refractory products
reduction of oxides by C ( SiO2, K2O, Na2O, B2O3)

imperfect assembly seal of the refractory parts
Tundish lining
Submerged nozzle
Prevention of alumina build up in submerged nozzles

The alumina build up is caused by a gaseous transfert of oxygen
The permeability of the refractory and the air tightness

of the assembly play an important part
Tundish lining
Submerged nozzle
Oxygen pick up and behaviour of submerged nozzle for

Al killed steels
Build up
Alumina build up
Beyond a certain air leakage, the

quantity of oxygen affect is so large
that it doesnt affect the Al in steel
Steel oxydation rate

Oxidation of
dissolved Al
Wear
Oxidation of liquid steel (Fe-C)

and corrosion of refractory by
iron oxydes and/or oxygen
The steel ther the carbon of the

nozzle are oxidized which cause
erosion
Tundish lining
Submerged nozzle
Oxydation of steel and wear of the submerged nozzle

The oxydation of steel causes the
oxydation of the carbon of the
submerged nozzle
We observe a significant erosion by
disintegration of the bonding phase.
The alumina particles are thus
drawn into the metal
This is a new source of
contamination by alumina of
refractory origin !
Tundish lining
Submerged nozzle
Exemple of a catastrophic wear

In extreme situation, the permeability of the refractory system
becomes very important and the submerged nozzle is damaged
Tundish lining
Submerged nozzle
Erosion of submerged nozzle / effect of the Al2O3-C refractory

no
erosion
High
erosion
Pure material
without silica
Material
with silica
Tundish lining
Submerged nozzle
Effect of steel grades on the behavior of the submerged nozzles

Steel grades
Clogging
Corrosion
decarburising
Mechanisms
Al killed
High
None
Moderate
Decarburation, oxidation of
aluminium , sticking of Al2O3
IFS
Erratic
Weak
High
Formation of Al2TiO5
Clogging/unclogging
Steel with SiCa

treatment
None
High
Moderate
Dissolution of alumina
aggregates and formation of
a low melting phase
High
Manganese
None
High
Moderate
Corrosion of alumina
aggregates with formation
of MnAl2O3
High
Phosphorus
None
High
Moderate
Corrosion of alumina
aggregates with formation
of aluminate of phosphate
High
carbon
Weak
None
Weak
Sticking of Al2O3 or
Interstitial free steel
Fe2+ (Fe3+,Al 3+) 2 O 4

Tundish lining
Submerged nozzle

1. Refractory solutions
improve the purity of Al2O3-C refractories with as little

silica and impurities as possible
reduce the permeability of the products
use internal layers to limit the clogging

o
Not permeable to gaseous exchange
Chemically inert with steel
Thermal shock resistant
Mechanically resistant to steel flow
A submerged nozzle with a carbon

free liner
Tundish lining
Submerged nozzle

2. Process and metallurgical solutions
To ensure perfect steel
cleanliness in the tundish
To avoid steel reoxidation between the sliding

gate of the steel ladle and the mould
Tundish lining
Submerged nozzle
PART II. (4.1.2) Corrosion, cleanliness and steel quality

INTERACTIONS OF REFRACTORIES AND STEEL DURING
THE PROCESS OF SECONDARY METALLURGY
I.1. Reactions between refractories, steel and slag
o Dissolution
o Dissociation/volatilization
o Oxydo-reduction / carbo reduction
o Formation of new compounds
o Combination of the refractory and a nondissolved element in steel
I.2. Metallurgical consequences
o Inclusionnary cleanliness
o Efficiency of Ca treatments of steel
o desulfurization
o Carbon pick up
Steel cord
Defects on the surface
The refractory- slag steel system in secondary metallurgy

Corrosion by slag :Dissolution
and erosion of refractory
Steel
ladle
Slag line
MgO-C
Reactive
Wall
Al2O3
Direct
transfert
Ref steel
Dissociation and
dissolution
slag
Spalling
Deposit of slag at the end

of the previous casting
Pollution of the slag
Pollution of the steel
Metallurgical consequences
Part 2 Dissolution
Volatilization Oxydo-reduct. Carbo-reduction New compounds Metallurgical impact
Some considerations about the slag chemistry and mineralogy

The slag behavior is very important in determining the steel quality
Study of phase assemblage with temperature
- mineralogical path
- microstructural changes
Exemple : basic oxygen furnace (BOF) slag

wt %
SiO2
TiO2
Al2O3
FeO
MnO
MgO
CaO
P2O5
LOI 1000C
12.8
0.7
1.4
18.4
2.9
5.2
52.4
2.3
0.3
Slag / MgO-C microstructure

Part 2 Dissolution
Basic oxygen furnace (BOF) slag
Thermodynamic prediction
100
SLAG
80
weight %
1650C : Slag + CaO(s)
Calcium silicates
70
Ca3SiO5 (C3S)
60
Ca2Si04 (C2S) + CaO
50
40
Calcium ferrite
Ca2SiO4
Ca2Fe2O5
Ca3SiO5
30
MgO
20
CaO
Ca2Fe2O5
10 MnO
MgO
Ca3MgAl4O10
0
0900
Ca3Ti2O7
1100
1300
1500
Minor phases
Fe(s)
1700
Decrease of the temperature
90
1900
T(C)
Part 2 Dissolution
Effect of thermal conditions on the kinetics

of cristallisation
1600C
10C/h
Rapid cooling
~ 3-5s
Small dendritic crystals

20-80 m
Industrial cooling
~ 24 -48h
Heterogeneous crystals.
50-150 m
Slow cooling
~ 72h
Homogeneous crystals
180-250 m
Size of crystals differs significantly depending on the cooling time:
a slow cooling promotes the growth of crystals

M. Gauthieu, J. Poirier, F Bodenan, G Franchescini, Wascon 2009
Par 2 Dissolution
Introducti
Volatilization Oxydo-reduct. Carbo-reduction New compounds Metallurgical

impact
Conclusi
An industrial example of interaction refractory/ slag

corrosion of MgO-C in steel ladles
Wear of the slag line

Dissolution/corrosion of MgO-C
Part 2 Dissolution
Correlations between metal cleanliness, corrosion mechanisms of

MgO-C in steel ladle and critical slag parameters
Steel types
Important wear
mechanism of MgO-C
Critical slag
parameters
Al deoxidized steels
Dissolution of magnesia
in CaO-Al2O3 slag
[CaO]/[Al2O3]
Dissolution of magnesia
in CaO-SiO2-Al2O3 slag
[SiO2]/[CaO]
Si deoxidized steels
Initial MgO
[Al2O3]
Slag TC
Ultra low [C] steels
Part2 Dissolution
Oxidation of carbon by
the slag iron oxide
[FeO]
Example : case of deoxidation with Al

Influence of the [CaO]/[Al2O3] ratio on the MgO saturation of
CaO-Al2O3 slags at 1600C and on the corrosion of MgO-C slag line
the variation of [CaO]/[Al2O3] has an important effect on wear

In the same time, the solubility of magnesia in the slag increases strongly
P Blumenfeld and Al. Effect of service conditions on wear mechanisms of steel ladle refractories Unitecr97 New Orleans
Part2 Dissolution
An industrial example of interaction refractory/ steel

spalling of bauxite walls
Observation of steel ladle lining degradations in service
16 heats : small crack in the lining
Part 2 Dissolution
24 heats : great evolution of the defect
Identification of the reactional mechanisms

Steel ladle
Slag
Chemical
Structural
penetration
dissolution
spalling
Several zones of attack with

different textures
Slag
Part2 Dissolution
Precipitation
zone
Impregnation
zone
Refractory
Evolution of the liquid composition at high temperature (1600C)

Slag
Precipitation zone
Impregnation
Refractory
90
Slag
Precipitation zone
Hexaaluminate
of lime
70
60
50
Corundum
Impregnation
Refractory
Mullite
Mullite
40
30
Mineral
phases
SiO2
Initial interface
Oxide content (wt %)
80
Profil of
composition of
liquid phase
Al2O3
20
10
CaO
Distance (mm)
0
-2
Part2 Dissolution
10
Reactions which contribute to degrading the steel quality

Dissolution
Volatilisation
Dissolution and
precipitation
Interactions
Steel /slag /refractory
Oxido reduction
Dissociation
Formation of new
compounds
Carbo reduction
Combination of the refractory and a
non-dissolved element in steel
Part 2 Dissolution
Direct dissolution
Chemical exchanges are controlled by a boundary layer
at the liquid/refractory interface
The gradient of composition is the driving force of the corrosion process
2 elementary steps : a thermochemical reaction at the solid/liquid interface and
a diffusion of species
Slag
Boundary
layer
Refractory
CArefractory
CAslag
Initial interface
Part 2 Dissolution Volatilization Oxydo-reduct. Carbo-reduction New compounds Metallurgical impact
Study of dissolution in laboratory

Dissolution of MgO in MgO-C refractory for
different times by CaO-SiO2 slag
[MgO] = f(t)
Slag
Steel
Slag
MgO
MgO % in slag
24
Saturation solubility of MgO
19
T = 1630C
14
slag CaO-SiO2 with

SiO2/CaO = 0.9
9
4
0
500 m
50
100
150
Time ( mn)
Slag/MgO interface
Dissolution with precipitation of new compounds

Heterogeneous mechanism with the precipitation of new phases
Decrease of the wear rate

Initial
interface
CBrefractory
CAslag
CAAB2/B
CBslag
CBAB/AB2
CAAB/AB2
CBAB2/B
CArefractory
Slag
Boundary
layer
Refractory
F. Qafssaoui, J. Poirier, J.P. Ildefonse, P. Hubert :Influence of liquid phase on corrosion behaviour of andalusite-based refractories. Refractories
Applications Transactions, 1 (2005) , 2-8
Transition between the different monomineral

layers : in bauxite and andalusite refractories
CA2 layer
CA2 : CaO-2Al2O3
CA6 : CaO-6Al2O3
CA6 layer
Corundum
layer
200 m
Bauxite brick
100 m
Andalusite brick
Corrosion of high alumina refractories by Al2O3-CaO slag, T=1600C
Dissolution precipitation processes inside a liquid phase

A slow precicipation from the a liquid phase
Dissociation, volatilization
Example : chromium volatilization of the magnesite-chrome lining
in RH/OB vacuum degazer
Vacuum = 10-3 atm
Overview of the brickwork of a vacuum degasser (RH/OB)

D. Brachet, F. Masse, J. Poirier, G. Provost : Refractories behaviour in the Sollac Dunkirk RH/OB steel degasser, Journal of the Canadian Ceramic
Society, 58 (1989), 61-66
Part 2 Dissolution Volatilization
Oxydo-reduct. Carbo-reduct. New compounds Metallurgical impact
Chrome pick up in steel

20 and 100 ppm of Cr in steel in correlation with oxygen blowing
Part 2 Dissolution Volatilization
Oxydo-reduct. Carbo-reduct. New compounds Metallurgical impact
Oxido-reduction
The reduction of oxides by the desoxidation metals occurs in the steel
Ex. SiO2 + Al => Al2O3 + Si

This table indicates the oxides which are reduced by desoxidation metals
Standard reference:
activity = 1
Part 2 DissolutionVolatilization Oxydo-reduction. Carbo-reduct. New compounds Metallurgical impact
Example of oxido-reduction reaction

Submerged nozzle in fused silica
The fracture of the tube occurs after one hour.
Silica was reduced by desoxidation elements (Al,Mn,Ca) presents in liquid steel

Other exemple of oxydo-reduction

Mechanisms
Driving force
Oxydo reduction
SiO2 dense layer

Coefficients of diffusion
aO2 / V
Slag
Key parameters
SiO2
SiC
CaO, MgO
K2O, Na2O
FeSi
G0 (T) :
3SiC + 2FeO 2 FeSi +SiO2 + 3C
Slag
SiO100m
2
SiC
Oxydation SiC
Rduction FeO
Carbo reduction
At high temperature, carbo reduction reactions occur in the oxide-carbon
refractories
Ex. SiO2 + C SiO (gas) + CO (gas) at 1550C

SiO2 + C Si (gas) + 2 CO (gas) at 1550C
Disappearance
of fused SiO2 aggregates
Microstructure of Al2O3-C refractory

used in continuous casting
100 m
C. Taffin, J. Poirier :The behaviour of metal additives in MgO-C and Al2O3-C refractories. Interceram International, 43 (1994), 356-358
Part 2 Dissolution Volatilization Oxydo-reduct Carbo-reduction New compounds Metallurgical impact
Formation of new compounds

Exemple : Al2O3-MgO in situ spinel castables
Impregnation zone
Slag
Impact
pad
- Multicomponent and heterogeneous

ceramic
- Microscopic observations at room
temperature
Al2O3-MgO castable corroded by a lime rich slag in a steel ladle

Part 2 Dissolution Volatilization Oxydo-reduct Carbo-reduct
New compounds
Metallurgical impact
Corrosion of MgO-Al2O3 castable by a lime rich slag

spinels
with the matrix : spinels

(Mg,Fe,Mn)O(Fe2Al2)O3
New compounds
Interaction between slag and matrix

(Mg,Fe,Mn)O(Fe2Al2)O3
Glassy
phase
SEM observation
Composition
and rate of slag and spinel (wt%)
composition and rate of slag and spinel (wt. %)
1
slag
P = 1 at.
T= 1600C
0,8
Al O (slag)
2
0,6
0,4
spinel
CaO(slag)
MgAl O (sp)
2
Al O (sp)
8
0,2
MnO(slag)
Fe O (slag)
2 3
FeO(slag)
MgO(slag)
0
0
0,2
12
0,4
<A>
<A>
0,6
New compounds
0,8
MnAl O (sp)
2 4
1
FeAl O (sp)
2
Interaction between slag and matrix

1
FeO
P = 1 at.
T= 1600C
Rate of
oxides in slag phase (wt
rate of oxides in slag phase (wt.%)
%)
0,8
Al O
2
0,6
MgO
MnO
0,4
0,2
0
0
0,2
0,4
<A>
<A>
0,6
0,8
Weight% of FeO, Al2O3, MgO and MnO in the liquide state

New compounds
Combination of the refractory and a non-dissolved element in steel

Far exemple, consider the reduction of the silica of the
refractory by the dissolved manganese in steel
2 Mn + SiO2 2 MnO + Si
MnO + SiO2 MnSiO3
Reoxydation of the steel
with the formation of solid
inclusions + glass
Quickly drawn
into steel
Formation of MnSiO3 crystals at the interface clay refractory / steel
New compounds
PART II. (4.1.2) Corrosion, cleanliness and steel quality

INTERACTIONS OF REFRACTORIES AND STEEL DURING
THE PROCESS OF SECONDARY METALLURGY
I.1. Reactions between refractories, steel and slag
o Dissolution
o Dissociation/volatilization
o Oxydo-reduction
o Carbo reduction
o Formation of new compounds
I.2. Metallurgical consequences
o Inclusionnary cleanliness
o Efficiency of Ca treatments of steel
o desulfurization
o Carbon pick up
Part 2
cleanliness O2 content
Inclusions of oxydes
Ca treatment Desulfurization Carbon pick up
Metallurgical consequences : inclusionnary cleanliness

Oxide cleanliness is measured by the total mass of
oxide inclusions formed in the liquid steel
Aluminum or silicon additions are used to transform
soluble oxygen into alumina (or silica)
Total dissolved oxygen contents :

Less than 20 ppm for Al killed steels
lower than 5 ppm for specialty steels
Inclusions of alumina
Structural steel
Part 2 Metallurgical impact cleanliness
O2 content
The dissolved oxygen content is directly converted

to a oxygen partial pressure
Part 2
Metallurgical impact cleanliness
O2 content
What consequences does this low oxygen partial pressure have

for the selection of refractories ?
To limit the possibility of oxygen pick up, the refractory s oxygen potential
must be lower than that of the steel
PO2 > 10-15at

Refractories
Cr2O3
SiO2
2 zones
PO2 = 10-15at
PO2 < 10-15at
Refractories
Al2O3
MgO
CaO
TiO2
1600C
Influence of the refractory material on the oxygen contents

Ar atmosphere
50 Kg induction furnace
and 3t ladle furnace
The refractory material

has a significant
influence on the oxygen
content of steel
Al Killed steel
at 1600C
Index of oxygen potential (in Kcal/mol O2)
Metal/Slag / Refractory reactions : spalling of Al2O3 refractory

lining and cleanliness of Si killed steels (steel cords)
Corrosion of
slag line
% MgO (slag)
MgO
Liquid silicates
+ MgO.Al2O3
Spalling
of walls
Al2O3
Precipitation of
MgO-Al2O3 oxydes
Hard inclusions
Liquid silicates
% Al2O3 (slag)
Oxide cleanliness can be affected by exogenous inclusions

from corrosion or erosion of refractories
Case of deoxidation with Si

Influence of CaO-SiO2-Al2O3 slag composition on the corrosion of
MgO-C with a temperature between 1600 and 1650C
The situation
is complex
with 3 cases
1.
Solid in suspension in Al2O3 poor slags slow corrosion
2.
Solids precipitated which MgO saturated in contact with the

refractory slow corrosion
3.
Totally liquid slag rapid corrosion
Metallurgical consequences : efficiency of Ca treatments of steel

Purpose
improving the castability of aluminum killed steels by transforming the
alumina deoxidation inclusions into liquid lime aluminate inclusions
Advantage
These liquid inclusions do not stick to the nozzle refractories
Before Ca treatment
After Ca treatment
Alumina
Al2O3
CaO
MnS sulphur
Silicoaluminates
Al2O3/SiO2/MnO
Part 2 Metallurgical impact
CaS
Globular calcic
inclusion
Impact refractories in the efficiency of Ca treatments of steel

Ca has a high affinity for oxygen
Possibility to reduce some constituents of the refractories
SiO2, Cr2O3, Al2O3, ..
Improvement in the efficency of a calcium tretment

when high alumina ladle refractories are replaced by
dolomite or magnesia refractories
Even with the use of basic refractories, possibility to a
transfer of magnesia towards the inclusions
Part 2
Composition of inclusions obtained by an too large

addition of SiCa to steel in a dolomite ladle
Transformation
path
Initial composition
of liquid inclusions
Final composition of
inclusions
55%MgO-35%CaO- 10%Al2O3
Solid at casting
temperature
Participate in nozzle
clogging
Formation of spinel inclusions in Al killed steels created by reaction of
the dolomitic lining with calcium addition in excess.
Metallurgical consequences : desulphurization

Obtained by metal slag
stirring in secondary metallurgy
Reaction of desulphurization
Requirements
Porus blocs in
a steel ladle
: CaO + S = CaS + O
liquid slag close

to lime saturation
Low oxygen
content in steel
For aluminum killed steels the final sulphur contents is less

than 10 and even 5 ppm !
Sulfur partition coefficient at equilibrium between liquid

slag of the CaO-Al2O3-SiO2-MgO system and steel
a (Al) = 0.03
1625C
+ 10% Al2O3 in slag
Final S
2 or 3
To obtain reproducible results in industrial conditions, it

is necessary to control well the slag composition
Effect of alumina and dolomite refractories on desulphurisation

Consequences : advanced desulphurization can only be
reached reliably and reproducibly in ladles with a basic lining
Alumina
Alumina
Dolomite
Richter and Wolf Plannenzustellung beim TN-Verfahren Document VDEh 1985

Effect of degree of lime saturation of the slag on desulphurisation

and refractory wear
Consequences : advanced desulphurization can only be
reached reliably and reproducibly in ladles with a basic lining
Best S conditions
Desulphurization
index
Refractory
wear
Lime saturation indexes smaller than 1 correspond to liquid slag

Bannenberg and Al. 6 Int. Iron and Steel congress, 1990, Nagoya
Part 2
Industrial applications: S vacuum treatment in basic ladles

Slag line
Refractory wear /
S treatment
[MgO]%
Sur
saturation
in CaO
Desulphurization index
Is = [CaO]/[CaO]s at the end of the treatment
Correlation between :
- the optimal desulfuration rate
- the slag composition
- the corrosion of the magnesia refractories
Metallurgical consequences : carbon pick up of ULC steel

Ultra-low carbon steel, such as intertitial free steel are elaborated
by metal-gas reaction under vacuum in oxidizing conditions
C
Mn
Si
Al
Ti
150
20
60
Typical chemical composition of a Ti-containing IF steel

for drawing applications (concentration in 10-3 % )
Mechanism of carbon transfert from MgO-C refractory to IF steel
ULC steel
Carbon pick up (ppm) in

steel ( after killed with Al)
Carbon pick up strongly varies with the composition of

the slag and the importance of argon stirring
Steel
ladle
16
14
Slag line
12
10
8
6
4
2
0
0
[Fe] (%) in slag
Relationship between carbon pick up and iron content in slag for a

ultra low carbon steel (killed Aluminium)
Mechanism of carbon transfert from MgO-C refractory to steel
ULC steel

Carbon pick up rises sharply when the slag is strongly

deoxidized and contains less than 2% of iron oxide
16
14
12
+ 10 ppm
C
10
8
6
4
2
0
0
[Fe] (%) in slag
Relationship between carbon pick up and iron content in slag for a ultra
low carbon steel (killed Aluminium)
Evolution of the carbon pick up of ULC steel
Carbon pick up
afiter deoxidation (ppm)
Strong correlation between carbon pick up of ULC steels

and MgO-C refractory wear rate of the ladle slag line
18
16
14
12
10
8
6
4
2
0
0
1
2
3
Mean wear rate of MgO-C slag line (mm/heat)
The wear of MgO-C slag line by the deoxidized slag plays

an important role in the transfert of carbon to steel
Mechanism of carbon transfert from MgO-C refractory to steel

Oxido reduction and vaporisation
of magnesium
C
At the interface , condensation of Mg(g)

Mg(g) + FeO MgO + Fe
Mg
MgO
0.2
Presence of iron
oxydes in slag
mm

16
14
12
Formation of a dense MgO layer

with a positive effect on the corrosion
10
8
6
4
2
Limitation of carbon pick up
0
0
[Fe] (%) in slag
Part 2
CONCLUSION
The refractory products are strategic for the

production of steel
They have a direct role on the quality of elaborated grades
chemical composition of the liquid steel
cleanliness : the amount and the nature of non metallic
inclusions
The prevention of defects concerning the steel surface
Prospects
The future evolutions of the refractory products
should be made by taking into account the
interactions : steel quality / refractory reactivity
In conjunction with metallurgists efforts to elaborate
clean steels, this improvement combines simultaneous
-control of refractory composition
-Porosity
-Permeability
-And reactivity
Thank you for

your attention

Impact of Refractories Corrosion On Industrial Processes: 4.1. Steel Making

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FIRE COURSE Unitecr2001, October 30th, 2011 Kyoto, Japan

FIRE COURSE Unitecr2001, October 30th, 2011 Kyoto, Japan

STEEL MAKING - CONTENTS OF THE PRESENTATION

Part II (4.1.2) : Corrosion, cleanliness and steel quality

Surface micrograph showing fine particles at

Steel challenge Cleanliness /chemistry

Non metallic elements

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

In particular, steel cleanliness and purity requirements make

Non metallic elements

Influence of non metallic elements on steel properties

Non metallic elements

More and more complex elaboration to eliminate

C content < 15 ppm

S content~ a few ppm

Lower limits of residual elements in steel making elaboration

Non metallic elements

The impact of refractory products on the quality of the metal

1. The possibility to keep the chemical composition of

Non metallic elements

The impact of refractory products on the quality of the metal

2. The achievement of the required metal cleanliness :

Non metallic elements

The impact of refractory products on the quality of the metal

3. The prevention of defects concerning the steel surface

Non metallic elements

Main classes of refractories in relation

Fired and unfired bricks

Non metallic elements

Main classes of refractories in relation

Magnesia-chrome and alumina unshaped products

Non metallic elements

Main classes of refractories in relation

Non metallic elements

Summary of different defect types in steel in relation

Inclusions and defects

Materials and assembly

PART 1. (4.1.1) FLOW CONTROL

Sliding gate system

The basic function : the control of metal flow rate

The plates of the sliding gate system

Effect of the plate cracks on the nitrogen pick up

Design of the plates of the sliding gate system

(a) cracks in a slide gate

In order to reduce cracking and to limit the re oxidation of the steel

The function : the control of metal flow rate

Sliding gate Stopper

The stopper may be a

Part 1. Continous casting

Sliding gate Stopper

A argon injection system in the stopper in order

Design to limit air

Sliding gate Stopper

The tundish lining

Part 1. Continous casting

Sliding gate Stopper

The tundish lining

Lining after use

Part 1. Continous casting

Sliding gate Stopper