International Journal of Engineering & Technology IJET-IJENS Vol: 10 No: 03

52

Molten Metal-Slag-Refractory Reactions

During Converting Process
Hady Efendy1, Mochamad Safarudin1, Haeryip Sihombing.2
Fakulti Kejuruteraan Mekanikal, Universiti Teknikal Malaysia (UTeM) Malaka, Malaysia
2
Fakulti Kejuruteraan Pembuatan, Universiti Teknikal Malaysia (UTeM) Malaka, Malaysia
1

Correspondance : hady@utem.edu.my

Abstract.Magnesiacarbon
(MgO-C)
refractories are widely used in converter
because of their favorable properties such as
low wetting by corrosive steelmaking slags
chemical compatibility with basic slags and
better thermal properties. The molten slag
is in contact with the refractory during the
converting process, where temperatures
>1450C are common. Local convection
currents develop near the slagrefractory
nickel metteair intersection that leads to
small-scale circulating flows that increase
dissolution. In this report the effects of
dissolution of MgO-C refractory samples
into nickel matte and Fe2O3-SiO2-MgO slag
were observation by optical microscope and
SEM/EDS. The experimental results show
that the rate of dissolution of MgO-C
refractory materials increased with the
temperature and immersion time. This
supports the assumption that the diffusion
of magnesium through the slag boundary
layer formed around the refractory samples
would be the rate-determining step. The
formation of a thin oxide layer at the
interface is due the reaction between
magnesium vapor and the CO generated by
the reaction MgO and C in the refractory
walls. The oxide inclusions formed in the
matte have been shown mainly to consist of
MgO, Fe2O3 and a mixture of them. The
rate
of
corrosion
increased
with
temperature and immersion time and
decreased when the slag was nearly
saturated with MgO. The experimental
results confirm the assumption that the
diffusion of magnesium oxide through the
slag phase boundary layer controls the
corrosion process. The corrosion mechanism
seems to be the dissolution of elements in the

refractory materials into the slag, followed

by penetration into the pores and grain
boundaries. Finally, grains are loosened
from the refractory into the slag.
Keywords: re-oxidation, converter, inclusions,
refractory, molten slag, corrosion rate, corrosion
mechanisms.

I. INTRODUCTION
The converter removes the remaining silica,
iron and iron oxide, which are referred to
collectively as slag from the nickel matte
product. This is achieved by heating the molten
matte and selectively oxidizing the iron by
blowing air through the molten liquid. The
oxidation of the iron is an exothermic reaction
and release heat into the converter. Silica flux is
added which melts and together with the iron
oxide forms converter slag. The addition of
scrap used to help control the temperature of the
converter content.
The converters are batch process. Furnace
nickel matte is put into the converter followed
by a quantity of flux material and scrap material
from which nickel is to be recovered. The
converter are then blown (air is blow into the
molten slag-matte batch through the tuyere
system). At the completion of each blow the
slag is poured out of the converters into ladles
for dumping. Then more furnace matte, scrap
and flux material is added, and the blowing
process is repeated. When the proportion of
nickel in the converter has risen to the required
level, the final high nickel converter slag is
poured off and finally the converter matte is
poured off and sent to the granulation system for
finally processing and packaging.

International Journal of Engineering & Technology IJET-IJENS Vol: 10 No: 03

The main chemical reactions in the converters

are:
2FeS + 2O2

FeO + xSiO2

2FeO + SO2
FeO (SiO2)x

(1)
(2)

During this procedure a coating is formed on

the refractory material. This coating is made of
slag coming from pellets dust and impurities.
As the thickness of the reaction layer increase
during time, the weight of the layer involve a
chipping off of big peaces of slag causing
damage to the refractory (peaces of brick crack
and stay fixed to the slag blocks). Due to this
phenomenon the converter has to be stopped
every year for a maintenance period. The
converter is then cleaned and the damaged bricks
are replaced. The replacement of the bricks is an
expensive operation and it involves the complete
stop of matte production that induces a big
overall cost. The composition of converters
matte is given in the following table 1:
TABLE 1.
THE COMPOSITION OF FURNACE NICKEL
MATTE

Ni
Co
Fe SiO2 MgO
S
0.173 0.027 18.7 45.5 22.5 0.22
Materials involved
This part will present the materials that have
been used in this study and give their main
properties: Bricks, Slag, SiO2 and Matte (The
composition was given in table 1).
Bricks
The Bricks used in the converters are made of
MgO-C refractory materials. Their composition
is given in table 2. The main proprieties needed
for refractory materials are their high heat
resistance, low thermal conductivity, mechanical
resistance, and thermal stresses resistance,
resistance to corrosion, resistance to erosion,
liquid and gas permeability [1].
TABLE 2.
THE COMPOSITION OF MGO-C BRICK

MgO Al2O3 CaO

58.4 8.3
0.7
Slag

SiO2 Cr2O3 Fe2O3 C

2.0 13.5 8.0 9.1

53

The slag, which forms on the walls of the

converter, is mainly constituted of disintegrated
furnace matte, silica and impurities. During the
converting process this FeS is transformed into
FeO. FeO is one of the stable oxide forms of
iron that is finding in nature (the other one is
magnetite). It got its name from a Greek word
meaning blood-like, because of its red color.
The slag is then constituted of FeO, impurities
coming from the brick, and SiO2 introduced by
the blowing. Its composition is given in the
following table 3:
TABLE 3.
THE COMPOSITION OF THE CONVERTER
SLAG

Ni
0.48

Co
0.22

Fe
51.9

SiO2
25.8

MgO
3.4

We can see in this chemical analysis that the

main impurities in the Slag after FeO are SiO2
and MgO. SiO2 is forming a glassy phase that
bounds the dust together and permits the slag to
enter into the pores of the refractory materials
and be fixed.
II. SAMPLE SOURCE AND PREPARATION
Magnesia-graphite Converter slag bricks were
recovered from brick piles after lining tear-out.
The compositions of these bricks were MgO-C
and slag coated samples were specifically
chosen to increase the odds of retaining slag line
reaction products. A typical post-mortem MgOC brick specimen from a converter slag line was
about 20 cm long and included a 10 to 25 mm
slag coating. Magnesia grains were generally
translucent and clear white at the slag-brick
interfaces and at the bottom (cold face) of the
bricks and blackened in the interior of the bricks.
The cold zones of the bricks were also loosely
held and disintegrated easily. The bricks were
sectioned perpendicular to the hot face, vacuum
impregnated with a low viscosity resin and cured
at 70oC. Both polished and polished thin sections
were made from the impregnated specimens.
The final polishing was completed with a
vibrating polisher with 1 to 0.5 micron diamond
paste and lapping oil.
The papers explained the mechanism
responsible for the penetration of slag into the

International Journal of Engineering & Technology IJET-IJENS Vol: 10 No: 03

brick and the different parameters that may

influence the degradation of the refractory.
Using SEM and optical microscopy the
influence of slag penetration on surface brick has
been studied and the resistance of the bricks
after using in the converting process. Than
concluded that a combination between diffusion
and infiltration of the slag was responsible of the
slag attack.
III.
OBSERVATION AND RESULTS
Infiltration of iron slag into refractory bricks
Because pores exist in a refractory, liquids
penetrate into refractory through the open pore
in contact with liquid. The mechanism of the
penetration differs a little according to the lining
orientation of the refractory or the pressure
applying on it, but the main driving force of
penetration is the suction of liquid like molten
slag due to capillarity. Figure 1 showing a depth
penetration of slag into refractory brick.
Wet ability between a refractory and a liquid
like molten slag is an important factor
influencing penetration. Also, surface energies
of refractory materials, surface tension of molten
slag, as well as interfacial energy between the
solid and liquid are factors related to penetration.
Basic refractories such as MgO which are easily
penetrated may be impregnated with tar or pitch
to fill the pores, so that residual carbon in the
pores prevents wetting by molten slag.

Figure 1. Depth Penetration Slag into

Refractory Brick

Slag coating

54

In contact with slag (Figure 2), a dense

spinell layer is formed in a first stage. This layer
becomes enriched very quickly in MgO on the
refractory side. It is completely transformed into
magnesia after several minutes.
Then the
thickness does not increase in time and remains
about 150 mm. The decarburized zone has a
much smaller thickness than for the nondeoxidized grade and it does not form a
continuous layer. Metal infiltrations in the
refractory have been observed, and they increase
with time. After application in steel making
process, a composition gradient of the
inclusionary cluster is observed with magnesia
on the refractory side.

Fig. 2. Photograpf of The Slag- MgO-C

Refractory Interface
At the working surface, the refractory is
eroded by molten FeO, while the back of the
refractory is decarburized by air. When the
working surface reached the carburized part, the
corrosion rate abruptly increases due to spalling.
The slag-refractory interface is characterized by
presence of metallic Fe beads and crystallization
spinel (MgAl2O4) crystal [2]. Metallic iron
beads at the interface are always associated with
graphite in the sample and often from oxidized
magnetite and hematite rims. Such association
indicates reduction of the FeO component of the
slag by graphite to from metallic Fe and CO gas
at the hot face of refractory. The following
reaction describes the observed behavior [3],
FeO(l) + C(s) => Fe(s) + CO(g)

(3)

Representative microstructures of the refractoryslag interface for a post-mortem MgO-C are

shown in Figure 2. Confirmation of dense layer
formation on the surface of the refractories was

International Journal of Engineering & Technology IJET-IJENS Vol: 10 No: 03

achieved by observation of the cross section of

the specimen after converter process (Figure 3
and Figure 4).

Slag

Refractory
MgO-C
Interface

Figure 3. Cross Section View of The MgO-C

Refractory Interface

Blocky and euhedral spinel crystals at the

interface exhibit and form an irregular and often
discontinuous chain-like structure.
IV.
DISCUSSION
The wear mechanism of refractory materials
by slag is complex phenomenon.
The
experimental results indicate that apart from
chemical attack of the slag an the MgO-C
refractory brick, penetration of the slag cause
serious direct loss of the MgO-C refractory
brick. The dissolution rate of MgO-C refractory
brick depends upon the some factor, such as
temperature converter process and viscosity slag.
The investigation of the sample after converter
process show, that there has been a formation of
inclusion on the molten metal. The inclusions
found in the molten metal were examined using
SEM/EDX.
The result showed that the
inclusions contained MgO. The formation of
spinel is practically a very significant aspect of
the reaction between MgO-C refractory and slag.
As the magnesium gas diffuses into the slag the
following reaction is taking place:
MgO.Al2O3(s) => Mg (s) + 2Al (s) + 4O

Fig. 4. Cross Section View Detail of The MgOC Refractory Interface

Interface
The slag-brick interface is characterized by
the presence of metallic Fe beads and
crystallization of euhedral spinel (MgO.Al2O3)
crystals. Metallic iron beads at the interface are
always associated with graphite in the brick and
often form oxidized magnetite and hematite
rims. Such association indicates reduction of the
FeO component of the slag by graphite to form
metallic Fe and CO gas at the hot face of the
brick. The following reaction describes the
observed behavior [3],
FeO(l) (in slag) + C(s) => Fe(s) + CO(g)

(4)

55

(5)

As the initial alloys did not contain any

magnesium, the presence of MgO in the
inclusions should indicate a result from the
contamination by the refractory/slag reaction.
The reaction MgO (s) + C (s) ==> Mg (g) +
CO (g) proceeds to the right at higher
temperatures and Mg(g) diffuses toward the free
surface of the sample where it encounter a
higher PO2[4]. Thereafter, magnesium is
oxidized to MgO, were it condenses and forms a
MgO layer. At the same time the CO (g) formed
during
MgO (s) reduction by carbon will
diffuses to the interface where it will react with
the molten slag forming MgO according to the
following reaction [5]:
Mg (s) + CO (g) ===> MgO (s) + C (s)

(6)

The reaction occurs immediately after the

reactive CO gas come into contact with the
surface of the slag. As a result, a thin oxide film
at MgO is formed at the interface.
The
formation of a surface layer will inhibit any

International Journal of Engineering & Technology IJET-IJENS Vol: 10 No: 03

further oxidation by CO, by retarding the

diffusion of carbon and oxygen a cross the layer.
The dissolution process in the refractory material
is supported by optical microscope and SEM
investigations of the samples.
The slag
penetrated the refractory material in pores and
crack. It is possible to observe that the slag
phase has a concentration gradient at the
boundary layer between slag/refractory. The
corrosion of oxide often occurs not by
dissolution or evaporation of the oxide, but by
the penetration of the solid by some all the
elements from the fluid slag [6]. The liquid
phase may be pulled into the open porosity of
the solid by capillary forces, and species from
the fluid will diffuse both down the grain
boundaries and into the bulk of the solid.
The higher wetting angle makes it more
difficult for the slags penetrate pores and crack
in the refractory. This is not the only think that
affects the infiltrating depth. The infiltrating
depth is also affected by the temperature
gradient in the brick. The temperature gradients
will cause the viscosity to increase and then the
infiltration depth will decrease.
V. CONCLUSIONS
During the production of nickel matte the
degree of oxide inclusions partly depends on the
reaction of the melt with the converter lining and
the pouring system. The refractory material may
be eroded by the molten steel and slag as well as
corroded through chemical reactions with the
slag and molten steel and the deoxidation
products. In this report of dissolution of MgO-C
refractory into CaO-Al2O3-SiO2-MgO slag were
examined after converting process. The results
show that the infiltration of slag into MgO-C
refractory and dissolution of MgO-C refractory
on the molten slag. This supports the assumption
that the diffusion of magnesium through the slag
boundary layer formed around the refractory
samples would be the rate-determining step. The
formation of a thin oxide layer at the interface is
due the reaction between magnesium vapor and
the CO generated by the reaction MgO and C in
the refractory walls. The oxide inclusions
formed in the steel have been shown mainly to
consist of MgO, Al2O3 and a mixture of them.

[1]

[2]

[3]

[4]

[5]

[6]

56

REFERENCES
N. P. Cheremisinoff, Handbook of
Ceramics and Composites, CRC Press,
1990, ISBN 0824780051
Chen Y., Brooks G., Nightingale S.,Slag
Line Dissolution of MgO Refractory,
Canadian Metalurgical, Vol.44, pp.323330, 2005
Camelli S., Labadie M.Analysisi of Wear
Mechanis of MgO-C Slag Line Bricks For
Steel Ladle, International FeuerfstKolloqium, Instituto Argentono de
Siderurgia, San Nicolas, Argentina, 2006
Watanabe A., Takahashi H., and Nakatami
F., Mechanism of Dense Magnesia Layer
Formation near Surface of MagnesiaCarbon Brick, J.Am.Ceram.Soc.69, pp
213-214, 1986.
Poirier J., Thillou B., Guiban M.A., and G.
Provost , Mechanism and
Countermeasures of Alumina Clogging in
Submerged Nozzles, 78th Steelmaking
Conf. Proc., Nasville, USA, Vol.78, pp
451-456, 1995
Cooper A.R., Kinetic of Refractory
Corrosion, Ceram.Eng. and Sci. Proc.,
No.2, pp 1063-1086, 1982