Chapter 5: MgO-C REFRACTORIES

1. BACKGROUND
The corrosion resistance of a refractory material that consists only of oxides can be improved
by reducing its porosity, i.e. increasing its density. However, when the porosity becomes too
low, the thermal shock resistance of the refractory is also low. The design of a refractory
material that has a high thermal shock resistance as well as excellent corrosion resistance is
therefore a matter of a delicate balance. Adding carbon to the oxide-based material solves the
problem, as carbon has low thermal expansion and high thermal conductivity (thereby
forming a material with high thermal shock resistance) and is not wettable by slags (thereby
increasing the corrosion resistance of the oxide-based material).
C-bonded bricks are primarily used in the steel industry. Carbon, as a bonding phase and as
graphite flakes, is added to basic bricks, alumina, zirconia and silica. Either a carbon bond
(derived from the pyrolysis of pitch ore resin) or a ceramic bond (derived from clay, or
metallic or ceramic additives) is used to bond the oxide and graphite in the oxide-graphite
refractories. High graphite levels are used to maximise thermal conductivity, whereby the
use of water cooling systems are facilitated. Oxide-graphite refractories may contain from 4-
30wt% natural graphite as well as carbon from the pitch or phenolic resin binder.

2. THE COMPOSITION OF MgO-C BRICKS

Magnesia-carbon bricks consist mainly of magnesia (sintered or fused grain) and graphite.
The graphite (in natural flake form) content usually varies from 5 to 16 mass%, but could be
higher in specific applications. Graphite prevents slag penetration and increases the thermal
conductivity and thermal shock resistance of the brick. Either an organic resin or pitch is
used as binder, which form a carbon bond during calcination. The binder therefore also
contributes to the carbon content of the brick. In addition to the main components, metals
such as Si, Al, Mg or Al-Mg is added to the mix. These metals / alloys are called anti-
oxidants, and are added to the mix to protect the graphite from premature oxidation during
service, which exposes the magnesia to corrosion by the slag. The metals / alloys are added
in the form of small particles to the raw material mix, and form part of the matrix of the
brick.

3. FACTORS WHICH CAUSE CHEMICAL WEAR OF MgO-C MATERIALS

The chemical wear and subsequent destruction of MgO-C refractory materials are mainly
caused by the oxidation of carbon, the high reactivity of magnesia crystals in contact with
graphite or carbon which results in the reduction and vaporisation of MgO, and slag
corrosion.

3.1 Oxidation of graphite

The oxidation of the graphite / carbon in the MgO-C brick is caused by the furnace
atmosphere itself (supply of CO2(g), O2(g)) and components in the slag (mainly FeO). This
results in the formation of a decarburised layer at the hot face, and the subsequent infiltration
of slag into this layer. The carbon-free zone is then susceptible to wear due to reactions
between the slag constituents and the impurities of the MgO and carbon sources, as well as
the magnesia grains. Many studies have shown that slag attack stop at the interface between
the carbon depleted and undepleted zones.
Since CO(g) and carbon stably exists inside the bricks, the partial CO pressure (PCO) is
approximately 1 atm., and carbon is neither oxidised nor eliminated inside the bricks. Along

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the hot face however, close to the corrosion front, the carbon in the brick is oxidised by the
iron oxides in the slag according to the reaction FeO + C(s) = Fe + CO. The Po2 at the hot
face is therefore set by the Fe-FeO equilibrium, and estimated to be ~10-8 atm. at 1600°C.
The oxygen partial pressure at the hot face is therefore much higher than inside the brick.

3.2 Reduction and evaporation of MgO

The phenomenon of the evaporation of magnesia and the subsequent textural deterioration of
the refractory constitute a principal factor of wear of the MgO-C bricks.
The reduction of MgO by carbon takes place behind the corrosion front, in the area where
the PCO~1 atm. and the Po2~10-16 atm. at 1600°C. This reaction leads to the formation of the
gaseous species Mg(g) with a partial pressure of PMg ~ 10-2 atm. at 1600°C. (The PMg
increases from ~10-6 to ~10-2 atm. as the Po2 decreases from 10-8 to 10-16 atm.) The Mg(g)
can diffuse from the reduction zone to the face adjacent to the source of heat where it
oxidises and recondenses to form MgO according to the reactions: Mg(g) + CO2(g) =
MgO(s) + CO(g) and Mg(g) + CO(g) = MgO(s) + C(s). A dense layer of MgO therefore
forms at the hot face of the MgO-C bricks, between the brick and the slag. This dense zone
of secondary magnesia limits the oxidation of carbon, hence maintaining a low porosity
whereby slag penetration is reduced. Behind this film the brick has acquired a porous
texture. Magnesia is thus redistributed through the refractory. The precipitated carbon
reduces FeO to Fe (less corrosive towards MgO), through the reaction FeO + C(s) = Fe +
CO(g). In addition the CO(g) formed by this reaction creates a slightly positive pressure in
the brick thus inhibiting further slag penetration. It also maintains a constant rate of
magnesia precipitation.

3.3 Infiltration of slag into decarbonised layer, and reaction between infiltrated slag
and MgO
Slag penetration into the MgO-C brick is a logical consequence of the formation of the
decarbonised layer due to an increase in the porosity of the brick. This results in the
dissolution of the phases that constitute the matrix, while the dissolution of the major MgO
crystals / grains is inherently slower. Dissolution of the matrix between the MgO grains
causes gradual debonding, which results in the loss of magnesia grains by washout, and the
subsequent chemical solution of the magnesia in the molten slag.

4. WAYS IN WHICH CHEMICAL WEAR CAN BE LIMITED

The main factors which influence the penetration and dissolution of MgO-C linings are: 1)
the purity of the starting materials; 2) the size of the grain; 3) the graphite content of the
brick; 4) wetting of the refractory by the liquid; 5) the addition of antioxidants; 6) the
temperature and atmospheric conditions; 6) the chemical and phase chemical compositions
of the refractory and slag (which determines the compatibility between the slag and
refractory); 7) the degree of porosity, the size and distribution of the pores.
For maximum refractoriness we have to simultaneously optimize the composition,
crystallinity and sizing of the grains, the composition, microstructure and quantity of the
matrix, the nature, technique and completeness of intergranular bonding as well as the
porosity and pore size distribution.

4.1 The use of high purity starting materials

Significant improvements in the slag corrosion resistance and in performance of magnesia-
graphite refractories can be achieved by using premium-quality refractories.

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Chemical impurities tend to concentrate as intergranular phases whereby a network of
relatively low melting point paths form, along which slags can easily penetrate. The
CaO/SiO2 ratio determines the temperature whereby a liquid phase starts forming (solidus
temperature) in the bricks.
Using a high purity magnesia product with very low boron oxide content can also reduce the
reactivity of MgO. B2O3 in the MgO accelerate the reduction of MgO due to the liquid
phase that forms in the CaO-B2O3 system that promotes mass transfer.
The oxidation of graphite can be reduced and the hot strength of the MgO-C refractory
improved by using high purity products. Graphite used in the refractories industry contains
variable amounts of impurities, commonly aluminosilicates. Silica containing minerals,
mullite and forsterite for example, are known to influence the development of the carbon
bond when the MgO-C refractories are fired.

4.2 The use of large grains

Another parameter governing the wear rate of the refractory is the size of the crystals that
make up the magnesia grains. In general the larger the grain size, the more difficult it is for
the slag to penetrate along grain boundaries and wash out individual crystals. The high
reactivity of magnesia crystals is also minimised by using large crystal size (e.g. fused)
magnesia. The oxidation of graphite can be reduced by using large flakes.

4.3 An increase in the graphite content of the brick

Increasing the amount of graphite contained in the MgO-C brick greatly increases the slag
corrosion resistance of magnesia refractories. This is due to the non-wettability of graphite,
the evolution of CO gas that retards slag infiltration into the brick matrix, as well as the
formation of a dense magnesia zone just behind the hot face of the MgO-C brick.
The role of graphite is similar to that of amorphous carbon, but brings some additional
improvements to magnesia refractories:
1. Oxidation resistance of large high-purity graphite flakes is much better than the oxidation
resistance of fine amorphous carbon.
2. Strength after coking is improved because strong bonds are formed between the carbon
from the resin and the edges of the flake graphite.
3. Low wettability of the slag to the graphite-containing refractories is at least partially
responsible for significantly improved slag resistance.
4. Graphite is responsible for increased thermal conductivity.
5. Thermal shock resistance is improved with increasing graphite content.

4.4 Wettability
Before the slag can attack / penetrate the refractory, the slag has to wet the refractory.
Further slag penetration depends primarily on the radius of the pores and the viscosity of the
slag. Once the slag has penetrated the refractory, the relevant phase diagrams can predict
the chemical interaction between the slag and refractory.

The first criterion for slag attack to take place is that the contact angle between the slag and
refractory should be small, as a low contact angle implies a high degree of wetting and vice
versa. A very low wetting angle signifies that the molecules / ions / atoms of the liquid are
attracted more to those of the solid than they are to each other. Graphite, because of its very
low surface tension, is responsible for the fact that slags do not easily wet MgO-C
refractories.

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A high degree of contact between the MgO grains result in a decrease in the wettability of
the periclase grains. It is therefore advantageous to use fused grain magnesia, where a high
degree of direct contact between the MgO crystals exists. The wettability of the magnesia
will also increase with an increase in the size and number of pores in the refractory.

4.5 The addition of antioxidants

The addition of carbon to oxide-based materials led to the question of how carbon can be
protected from oxidation. This has been addressed by adding non-oxides such as metal,
alloy and carbide particles to the refractory mixture, where they perform a self-repairing
function. These non-oxides include Al, Si, Al-Si, Al-Mg alloy, SiC, B4C and Si3N4, and are
called anti-oxidants. The main purpose of an antioxidant is to protect all forms of carbon
(graphite or the binding carbon) in the MgO-C brick, since this is the most vulnerable part of
the refractory structure in high chemical and mechanical wear areas. Metal additions also
play a role in the development of high temperature bonds and impart resistance to oxidation
and slag attack by blocking and modifying the pore network. A successful antioxidant will
therefore capture free oxygen whereby carbon is protected from oxidation, it will also reduce
the aggressive oxides such as iron oxide, whereby chemical attack on the refractory is
decreased. In turn this will lead to the strengthening and densification of the MgO-graphite
matrix without negatively affecting the mechanical and chemical properties of the MgO-C
products. Metallic carbides are also formed between the metallic antioxidant and carbon,
which create ‘bridges’ within the matrix of the brick, resulting in improved hot strength.

Al, Mg and Si are most frequently used as antioxidants in magnesia-graphite refractories.

The effectiveness of metals as antioxidants are in the order Si, Al and Mg. Mg is also the
most effective at the lowest temperatures, but very dangerous to handle.

Aluminium as antioxidant
When Al alone is used as antioxidant it protects the matrix by absorbing oxygen, forming
initially the oxide according to the reaction: 2Al + 3CO(g) = Al2O3(s) + 3C(s), and then
spinel (MgAl2O4), which is the stable and final product at high temperatures at the hot face.
The only stable gas is Al2O, which forms under strongly reducing conditions at temperatures
above 1557°C. Suppression effects of Al on oxidation are due to a decrease in oxygen
supply rate due to the densification of the decarbonized layer which efficiently preclude gas
and slag penetration. Al is however, not reactive below 1000°C. Consequently, when the
resin binder thermally decompose, no chemical or ceramic bond will be formed in the
matrix. At higher temperatures (900-1300°C) aluminium combines with carbon to form
carbides, which has a strong tendency to hydrate at ambient temperature according to the
reaction Al4C3 + 12H2O = 3CH4 + 4Al(OH)3. This hydration reaction causes crack
formation, especially during operational shutdowns. Al4C3 is reported to decompose above
1500°C and form spinel. AlN can also form, but is only stable at lower temperatures.
Silicon can be added to the system to suppress carbide formation, but this can lead to the
formation of low melting point, complex silicate species that can act as slag generators.

Silicon as antioxidant
Silicon additions yield forsterite at the hot face (carbon free zone), while SiC (above
1000°C) and Si3N4 form at depth into the refractory. The only stable gas is SiO, which
forms under reducing conditions.

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Magnesium as antioxidant
With Mg addition MgO is stable at the hot face. Mg3N2 can be formed, but is only stable
below 1300°C, and hydrates while releasing ammonia (NH4OH).

Al-Mg alloys as antioxidants

The use of Al-Mg alloys minimizes the problems that are associated with only using Al.
The alloy has a lower melting point than Al and is therefore more reactive at low
temperatures, i.e. below 1000°C. Due to the high partial pressure of CO(g) inside the brick,
metallic aluminium and magnesium vapours react with CO(g) to form spinel, magnesia and
precipitate carbon: 2Al:Mg(g) + 5CO(g) = MgAl2O4 + MgO(s) + 5C(s). Spinels deposit in-
situ, thus densifying the matrix, while magnesia is preferentially deposited at the hot face.
Through this reaction the decarburisation of the slag / brick interface is significantly
reduced. The intimate relation between Al and Mg in the alloy is important in suppressing
extensive reactions of Al with primary magnesia grains. Spinel is instead formed in the
intergranular spaces. Since part of the alloy is metallic Mg, the resulting secondary oxide
deposits frequently crystallize on the primary grains to form bridges between the coarse and
fine magnesia grains. This is an important factor in maintaining strength and cohesion in the
matrix, even when all the carbon has been oxidised. In the Al-Mg alloys the Mg also
suppresses the tendency of aluminium to react with carbon to form carbides. This increases
the hydration resistance of the refractory and controls the formation of microcracks due to
the conversion of aluminium carbide to aluminium hydroxide during maintenance of the
lining.

4.6 Atmospheric conditions and temperature

Refractory wear is limited by keeping the operating conditions reducing, and by preventing
excessively high operating temperatures. Increasing operating temperatures invariably
accelerates slag attack since the viscosity of the slag and its reaction products are reduced,
and the kinetics of the chemical reactions involved are accelerated.

4.7 Slag chemistry

The slag, which is contained in a MgO-C lined vessel, should be saturated with MgO in
order to minimize chemical wear of the lining. If this criterion is not adhered to, the amount
of MgO which will be taken from the lining could be high, as equilibrium conditions are
approached during extensive stirring and long holding times.

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