International Journal of Engineering & Technology IJET-IJENS Vol:10 No:03 40

103303-8787 IJET-IJENS June 2010 IJENS

I J E N S
Molten Metal-Slag-Refractory Reactions
During Converting Process

Hady Efendy
1
, Mochamad Safarudin
1
, Haeryip Sihombing.
2

1
Fakulti Kejuruteraan Mekanikal, Universiti Teknikal Malaysia (UTeM) Malaka, Malaysia
2
Fakulti Kejuruteraan Pembuatan, Universiti Teknikal Malaysia (UTeM) Malaka, Malaysia
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 Fe
2
O
3
-SiO
2
-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, Fe
2
O
3

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.

I ndex Term-- 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.
The main chemical reactions in the converters are:

2FeS + 2O
2
2FeO + SO
2
(1)
FeO + xSiO
2
FeO (SiO
2
)
x
(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 I:

TABLE I
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,
SiO
2
and Matte (The composition was given in table I).

Bricks
The Bricks used in the converters are made of MgO-C
refractory materials. Their composition is given in table II.
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].







International Journal of Engineering & Technology IJET-IJENS Vol:10 No:03 41
103303-8787 IJET-IJENS June 2010 IJENS
I J E N S
TABLE II
THE COMPOSITION OF MGO-C BRICK

MgO

Al
2
O
3

CaO
SiO
2


Cr
2
O
3


Fe
2
O
3

C
58.4 8.3 0.7 2.0 13.5 8.0
9.1
Slag
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 SiO
2
introduced by
the blowing. Its composition is given in the following table
III:

TABLE III
THE COMPOSITION OF THE CONVERTER SLAG
Ni Co Fe SiO2 MgO
0.48 0.22 51.9 25.8 3.4

We can see in this chemical analys is that the main
impurities in the Slag after FeO are SiO
2
and MgO. SiO
2
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 pos t-mortem MgO-C 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 70
o
C.
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 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 s uction
of liquid like molten slag due to capillarity. Fig. 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.


Fig. 1. Dept h Penet rat ion Slag int o Refract ory Brick


Slag coating
In contact with slag (Fig. 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 non-deoxidized 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. Phot ograpf of The Slag- MgO-C Refract ory Int erface

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 (MgAl
2
O
4
)
crystal [2]. Metallic iron beads at the interface are always
International Journal of Engineering & Technology IJET-IJENS Vol:10 No:03 42
103303-8787 IJET-IJENS June 2010 IJENS
I J E N S
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 refractory-slag
interface for a post-mortem MgO-C are shown in Fig. 2.
Confirmation of dense layer formation on the surface of the
refractories was achieved by observation of the cross section
of the specimen after converter process (Fig. 3 and Fig. 4).


Fig. 3. Cross Sect ion View of The MgO-C Refract ory Int erface


Fig. 4. Cross Sect ion View Det ail of The MgO-C Refract ory Int erface

Interface
The slag-brick interface is characterized by the presence
of metallic Fe beads and crystallization of euhedral spinel
(MgO.Al
2
O
3
) 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)
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.Al
2
O
3
(s) => Mg (s) + 2Al (s) + 4O (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 PO
2
[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 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
Interface
Refractory
MgO-C
Slag
International Journal of Engineering & Technology IJET-IJENS Vol:10 No:03 43
103303-8787 IJET-IJENS June 2010 IJENS
I J E N S
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-Al
2
O
3
-
SiO
2
-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, Al
2
O
3
and a mixture of
them.

REFERENCES
[1] N. P. Cheremisinoff, Handbook of Ceramics and Composites, CRC Press,
1990, ISBN 0824780051
[2] Chen Y., Brooks G., Night ingale S.,Slag Line Dissolut ion of MgO
Refract ory, Canadian Met alurgical, Vol.44, pp.323-330, 2005
[3] Camelli S., Labadie M.Analysisi of Wear Mechanis of MgO-C Slag Line
Bricks For St eel Ladle, Int ernat ional Feuerfst -Kolloqium, Inst it ut o
Argent ono de Siderurgia, San Nicolas, Argent ina, 2006
[4] Wat anabe A., Takahashi H., and Nakat ami F., Mechanism of Dense
Magnesia Layer Format ion near Surface of Magnesia-Carbon Brick,
J.Am.Ceram.Soc.69, pp 213-214, 1986.
[5] Poirier J., Thillou B., Guiban M.A., and G. Provost , Mechanism and
Count ermeasures of Alumina Clogging in Submerged Nozzles, 78
th

Steelmaking Conf. Proc., Nasville, USA, Vol.78, pp 451-456, 1995
[6] Cooper A.R., Kinet ic of Refract ory Corrosion, Ceram.Eng. and Sci.
Proc., No.2, pp 1063-1086, 1982