ANALYSIS OF THE WEAR MECHANISM OF MgO-C SLAG LINE BRICKS FOR STEEL

LADLES

Silvia Camelli*, Instituto Argentino de Siderurgia, San Nicolas, Argentina

Marcelo Labadie, Siderar, San Nicolas, Argentina

ABSTRACT microstructural aspects and phases of different chemical

The main wear mechanisms of the refractory ladle slag composition.
line are chemical corrosion and mechanical erosion due to -Layer I, with a thickness of 2,2 mm, is formed by
stirring of the steel bath. The chemical potential difference magnesium oxide dendrite crystal, iron and calcium
between the refractory and the slag under high temperature aluminate needles and calcium aluminium silicate crystals.
conditions is the driving force for the chemical wear All of these are immersed in a calcium aluminate matrix
mechanism. (figure 3).
The objective of this work was to analyse the wear -Layer II. Its thickness is 3 mm and is composed of
mechanism of MgO-C brick at the steel ladle slag line. magnesium altered crystals by iron and manganese,
A post mortem study was performed through optical different content of calcium, iron and titanium
and electronic microscopy (SEM) and EDS analysis. By aluminosilicate crystals, calcium-magnesium-iron
using these techniques glaze characteristics and the slag- aluminates and calcium silicate crystals. These phases are
refractory interaction were determined. Also, immersed in a calcium aluminate matrix (figure 4).
microstructural changes in the bricks were evaluated.
The identified attack mechanisms were: graphite Tab. 1 Properties of MgO-C bricks used in Siderar slag
oxidation, slag penetration into the matrix and around the line ladle
MgO grains, magnesia-wüstite formation, loosening of Apparent density (g/cm3 ) 2.93 ± 0.01
MgO grains and finally dissolution of MgO grains into the Apparent porosity (%) 4.8 ± 0.1
slag. Apparent density after heating at 1150°C
2.86 ± 0.05
in reduction atmosphere (g/cm3 )
INTRODUCTION Apparent porosity after heating at 1150°C
The main wear mechanisms of the refractory ladle slag 11.1 ± 0.1
in reduction atmosphere (%)
line are chemical corrosion and mechanical erosion due to Decarburized thickness (mm) 4
stirring of the steel bath [1]. The corrosion process is a Cold crushing strength (MPa) 28 ± 4
function of many variables including temperature, Periclase (MgO) ü
refractory composition, slag viscosity, slag composition Crystalline phases Graphite (C) ü
and degree of agitation. ü
Aluminium (Al)
The working lining in Siderar ladles is composed of
two different types of bricks: MgO-C in the slag line and
Al2 O3 -MgO-C in the walls and bottom. The average
lifespan of brick slag line is 95 heats.
The objective of this work was to analyse the wear
mechanism of MgO-C brick at the steel ladle slag line.
A post mortem study was performed through optical
and electronic microscopy (SEM) and EDS analysis. By
using these techniques glaze characteristics and the slag-
refractory interaction were determined. Also,
microstructural changes inside the brick were evaluated.

EXPERIMENTAL
The properties of slag line ladle MgO-C bricks as
received are presented in table 1 [2].
The post mortem aspects of the MgO-C brick together Fig.1. Post mortem MgO-C slag line brick used in steel
with the analyzed sample for microstructural study are ladle.
shown in figure 1.
The post mortem study was carried out by optical and
electronic microscopy (SEM) and EDS analysis. This
study allowed us to determine the slag characteristics on
the hot face brick, the slag and the refractory interaction
and brick microstructure changes.

Slag
The slag thickness varies between 4 and 6 mm (figure
2). The slag layer shows pores, steel drops and two
different layers. These layers contain distinctive

Fig.2. Slag layer and MgO-C brick interface.

 grains. This interaction promotes low temperature phases
formation and facilitates the crystal loosening.

Mg

Mg

Al Ca

Fig.3. Ele ments distribution in slag layer I.

Fe Ca

Fig.6. MgO grains indirect corrosion.

Slag - MgO-C brick matrix

The microstructural analysis permitted observed the
decarburized MgO-C brick matrix in contact with slag
(figure 7). The interface between the slag and the brick is
Mg shown in figure 8. Spinel crystals were formed in the
MgO-C brick matrix. Also, calcium silicate crystals were
identified in the brick matrix.

Fe Ca

Fig. 4. Ele ments distribution in slag layer II.

Sequential EDS analysis of the different elements in Fig. 7. Decarburized matrix and slag interface
two slag layers is presented in figure 5.

50
MgO
Al2O3
45
SiO2
CaO
40 FeO
MnO

35

30
Components (%)

25

20

15

10

0
0 1 2 3 4 5 6
Distance from brick hot face (mm)

Fig. 5. Elements evolution in the both slag layers.

Al Mg
Slag – MgO grains interaction
Near the interface between slag and MgO-C brick, Fig. 8. Elements distribution in the MgO-C brick hot face.
MgO grains loosening from the brick and immersed in slag
were identified. Elements distribution in this area is shown DISCUSIÓN
in figure 6. In that area it is possible to observe the The first slag layer is composed of a calcium aluminate
corrosion of the grains due to their interaction with iron matrix with 1400 °C melting point (phase equilibrium
oxide and manganese oxide. The slag penetrates into the diagram for Al2 O3 – CaO – FeO system) and different
intragranular silicate bond of the sintered and fused MgO crystals:
* iron and calcium aluminate, with softening temperature refractory material and form the corresponding reaction
of 1336°C (phase equilibrium diagram for Al2 O3 – CaO – products [4].
FeO system)
* calcium and aluminum silicate (gehlenite), with 100

softening temperature of 1380°C (phase equilibrium 90

MgO
CaO
FeO
diagram for Al2 O3 – CaO –SiO2 sytem). 80 MnO

* dendrite MgO 70

Chemical composition of the first slag layer is 60

Components (%)
presented in figure 8. This diagram shows that the slag is 50

completely liquid at 1600°C, and therefore it is not 40

saturated with periclase. 30

In table 2, slag ladle furnace chemical composition is

20

presented. This slag sample was taken previous to the end

10
of the ladle campaign. Such slag, like in the first slag layer
0
on MgO-C brick, is liquid and it is not saturated with MgO 0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 5 5,5
Distance from brick hot face (mm)

at 1600°C.
Fig. 9. EDS analysis in MgO grains in slag thickness.

Slag chemical composition of the second layer is

presented in figure 10. This slag is saturated with
magnesium oxide at 1600°C.
Table 3 shows the chemical comp osition of ladle slag
before the treatment in the ladle furnace.

Fig. 8. Phase equilibrium diagram for Al2 O3 – CaO –SiO2

10%MgO system [3].

Tab. 2. One slag furnace ladle chemical composition

SiO2 MnO FeO MgO CaO Al2 O3
(%) (%) (%) (%) (%) (%)
LF slag 4,5 1,1 1,0 9,3 54,0 32,7

The second slag layer adhered to MgO-C brick Fig. 10. Phase equilibrium diagram for CaO-MgO-SiO2 -
contains a higher level of iron oxide than the first slag 35% Al2 O3 system [3].
layer. Also, the second slag layer has lower calcium oxide
content than the slag layer as is shown in figure 5. Tab. 3. Chemical composition of slag ladle before the
The second slag layer is composed of calcium treatment in the ladle furnace.
aluminate as a matrix and different types of crystals: SiO2 MnO FeO MgO CaO Al2 O3
*calcium, titanium, iron and aluminium silicates with (%) (%) (%) (%) (%) (%)
different contents of these elements with 1400 – 1500 °C Slag 4,3 2,7 2,6 9,5 44,8 31,1
melting point .
*calcium and aluminum silicate with 1450°C melting point Both slag layers identified on slag line post mortem
(phase equilibrium diagram for Al2 O3 – CaO –SiO2 MgO-C brick are aggressive to the refractory material
system) lining.
* different content of calcium, magnesium and iron * The first slag layer, corresponding to the slag of the
aluminates end of the treatment in the ladle furnace (fig. 8), is not
*attacked MgO crystal by iron oxide in the first place and saturated with magnesium oxide and is completely liquid
by manganese oxide and calcium oxide afterwards (figure at the process temperature. It is widely known that these
9). This mechanism is the result of Fe, Mn and Ca being conditions are the main causes of corrosion and lining
the slag elements that diffuse more rapidly into the wear [5, 6].
* The second slag layer, corresponding to the ladle slag
previous to ladle furnace treatment (figure 10), is saturated
with periclase but contains a higher level of iron oxide.
This oxide increases slag fluidity – break down the slag
silicate network – and promotes the brick matrix
decarburizing, as shown:
FeO + C Fe + CO (I)
The graphite oxidation increases the brick porosity,
allowing slag penetration to the system, followed by the
dispersion of periclase grain in the slag.
Moreover, the iron diffuses into MgO grain and
promotes magnesia – wüstite formation. This new phase
decreases MgO grain refractoriness and also delays the
wear speed of the refractory material. This mechanism is
known as MgO grain indirect dissolution. Such passive
corrosion is the typical mechanism in BOF MgO-C brick,
where iron oxide in slag steelmaking is superior to 18% [7,
8].
Previous research has shown that the common indirect
corrosion mechanism in slag line MgO-C bricks results in
spinel (Al2 O3 .MgO) formation at slag-refractory interface.
This new phase is a barrier to aggressive agents, putting
refractory dissolution off [9].
Different components were identified in the MgO-C
brick: graphite fibres, fused MgO, sintered MgO and
resultant products of aluminium oxidation (antioxide
agent). The latter forms aluminum carbide, aluminum
oxide and A l2 O3 .MgO spinel, according to oxygen partial
pressure and temperature inside the brick [10].
CONCLUSIONS
The post mortem study was carried out through optical
and electronic microscopy (SEM) and EDS analysis,
allowed identification of slag - brick adherence
characteristics, MgO-C refractory wear mechanism and the
microstructural changes inside the brick.
Slag on the brick hot face is composed of two different
layers. These layers contain distinctive microstructural
aspects and different chemical composition phases. Both
layers are aggressive to the refractory material lining
because:
*the first slag layer is not saturated with MgO and it is
completely liquid at the process temperature. This slag
corresponds to the slag at the end of the treatment in the
furnace ladle.
* the second slag layer is saturated with MgO, but contains
a high level of iron oxide content. This slag corresponds to
the ladle slag previous to furnace ladle treatment.
The identified attack mechanisms were: graphite
oxidation, slag penetration into the matrix and around the
MgO grains, magnesia-wüstite formation, loosening of
MgO grains and finally dissolution of MgO grains into the
slag.
The indirect corrosion process with magnesia-wüstite
formation is not a typical damage mechanism in ladle slag
line MgO-C brick. This mechanism is a common corrosion
process in BOF and electric arc furnace MgO-C brick,
where slag oxidation is higher.
Al2 O3 . MgO spinel in the slag - MgO-C brick interface
was not identified.
Magnesia-wüstite formation at MgO-C brick hot face
suggests that slag during the laddle campaign contains
high iron oxide levels that allowed a new phase formation.
Iron oxide sources result from BOF slag or recycled slag
used in the ladle.
REFERENCES
[1] Oliveira S, Escórias e mecanismos de desgaste de
refractários para forno panela; Curso de ALAFAR,
“Fundamentos, operación y refractarios para hornos
cuchara”; 1997; Bs. As., Argentina.
[2] Gorosurreta C, Brandaleze E, Camelli S, Topolevsky R
Labadie M. Caracterización de ladrillos refractarios de
MgO-C. SAM/CONAMET 2005 Proceedings; Mar del
Plata, Argentina.
[3] Allibert M, Gaye H, Geiseler J, Keene B, Janke D,
Kirner D, et al. Slag Atlas, 2nd Edition, Germany, Ed.
VDEh; 1995.
[4] Lee W, Zhang S. Direct and Indirect slag Corrosion of
oxide and oxide – C Refractories. VII International
Conference on Molten Slags Fluxes and Salts
Proceedings; 2004, pp. 309 – 319.
[5] Rigaud M, Landy R. Pneumatic Steelmaking. Volume
Three, Refratories, Warrendale, Ed. Iron & Steel
Society; 1996
[6] Lee, M , Strezov L, Goldswothy D, Simpson I, Murgas
I, Jahanshshsi S. Implementation of a Thermodynamic
Model for Slag – Refractory Interaction in ladle and
tundish and for inclusión Engineering. Scaninject VII.
Part I. 7th International Conference on Refining
Processes; 1988, pp. 123 - 148
[7] Camelli S. Mecanismos de adherencia de escoria al
revestimiento refractario de convertidores al oxígeno,
Tesis de Maestría, Universidad de Buenos Aires; 2004.
[8] Camelli S, Madias J, Brandaleze E, Bentancour M,
Topolevsky R. Slag - refractory adherence mechanism.
44th International Colloquium on Refractories -
Septiembre 2001, Aachen, Alemanis
[9] Chen Y,Brooks G, Nightingale S. Slag line dissolution
of MgO refractory. Canadian Metallurgical; 2005, Vol.
44, N°3, pp. 323-330.
[10] Yamaguchi A. Thermochemical Analysis for
Reaction Processes of Aluminium and Aluminium –
compounds in Carbon-containing Refractories; 1997,
Taikabutsu Overseas, Vol.17 No 2.