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Materials Today: Proceedings 5 (2018) 2359–2366 www.materialstoday.com/proceedings

ICMS 2017

Raw materials for manufacturing of Superior quality MgO-C bricks

Manish Kumar Kujur *, Indranil Roy, Kaushlesh Kumar, Purimetla Chintaiah,
Somnath Ghosh, Nirmal Kanti Ghosh
R & D Centre for Iron and Steel, SAIL,Ranchi,Jharkhand-834002,India

Abstract

In SAIL Plant, Magnesia carbon (MgO-C) bricks are used as lining material for Metallurgical Vessels like Steel ladles as well as
Basic Oxygen Furnaces (BOF). MgO-C bricks are the most suitable refractory in these conditions for slag line as they possess
superior slag penetration resistance and excellent thermal shock resistance at elevated temperature. In Iron & Steel Industry,
manufacturing processes has changed significantly due to the rising demand of quality steel in the market. Furnace capacities
have increased & technological parameters have changed. Plants have been modernized with addition of secondary steel making
facilities to meet the stringent quality requirement of newer grades of steel.
Refractories in steel ladle are subjected to severe operating conditions like high temperature (1670-17000C) tapping of liquid
steel from BOF, thermal shock, abrasion with molten metal due to stirring during gas purging, localized heating in slag zone due
to arcing, corrosion with slag, thermo mechanical stress etc. Hence, use of superior quality refractory material with evenly
distributed impurities is essential to get an end product of very high corrosion and spalling resistance and high thermo-
mechanical properties. Easier application technique is also required for higher lining life with less down time. Various qualities
of magnesia carbon refractories are used in different zones of steel ladles & BOF. Magnesia carbon refractories are essentially
constitute of two highly refractory components i.e. magnesia and graphite.
Sea water magnesia is mainly used in SAIL as the main raw material for manufacturing of magnesia carbon bricks. Fused
magnesia has also been tried by partially mixing with sea water magnesia. Although MgO content in magnesia is important up to
a certain level, but the type of impurities and their relative proportions plays vital role in achieving good performance. Besides
chemical purity, bulk density and crystal size are considered to be very important properties of magnesia for application in BOF
and steel ladles. Beside magnesia, graphite of both indigenous and import sources were used in different occasions. Purity of
graphite has been reported to have great influence on slag corrosion resistance and hot properties of magnesia carbon bricks.
Particle size distribution of graphite influences porosity and thermal shock resistance properties of magnesia carbon bricks.
This paper deals with the properties of different raw materials for making of superior quality MgO-C bricks for improved
performance in Metallurgical vessels of SAIL plants.

* Corresponding author. Tel.: +91-651-241-1145; fax: +91-651-241-1072

E-mail address: [email protected]

2214-7853© 2017 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of Second International Conference on Materials Science (ICMS2017).
2360 Manish Kumar Kujur et. al. / Materials Today: Proceedings 5 (2018) 2359–2366

© 2017 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of Second International Conference on Materials Science (ICMS2017).

Keywords: Magnesia; Graphite; Steel Ladles; Basic Oxygen Furnace.

1. Introduction

In Steel Melting shop of Iron & Steel Plants; liquid iron comes from Blast Furnaces and processed in Basic Oxygen
Furnace (BOF) to convert liquid iron to liquid steel. This liquid steel is further processed through Secondary
Refining units consisting of Ladle Furnaces and other vacuum furnaces like Vacuum Argon Degassing, Vacuum
Oxygen Degassing or Ruhrstahl Heraeus (RH) Furnaces. In these furnaces; required chemistry of steel is achieved
by addition of different additives maintaining the thermal profile of the liquid steel. These processes involve
vigorous arching and purging. Further the passed grade is sent to continuous casting shop for casting of billets,
blooms or slabs of the required sizes. In these refining units liquid steel is transported in a metallurgical container
called ladles. These metallurgical vessels and containers need to be lined with superior quality refractory with an
ability to sustain different thermo-mechanical and thermo-chemical stresses.

1.1 Magnesia - Carbon

Magnesia-carbon refractories are unfired refractories and essentially constituted of high purity magnesia grains and
graphite bonded by a liquid binder. The idea of adding carbon, in refractory originally stemmed from the observation
that carbon is not easily wetted by slag. Thus carbon can prevent slag from entering the brick and eroding the
magnesia. This concept was well established with conventional tar/pitch bonded Basic Oxygen Furnace (BOF) brick
with carbon levels 2.5 to 5%. Brick of this type were used quite successfully in basic BOF for a number of years.
The conventional tar/pitch bonded magnesia brick can be thought of as a magnesia brick that contains just enough
carbon to fill the pore structure. However, as one increases the carbon content beyond 5%, it is no longer nearly a
pore filling. It creates a refractory where carbon addition in many ways dictates the brick properties and thus led to
the development of series of new generation of MgO-C refractory bricks. Magnesia-carbon bricks can contain
carbon as high as 30% but in ladles, it generally contains carbon up to 12%.

As there is no mutual interaction between magnesia and graphite, liquid resin or pitch is used as binding material.
This liquid binder plays an important role by providing strength at low temperature and also at high temperature by
forming carbon network. As carbon is easily oxidized at high temperature, certain metal powders are added to inhibit
oxidation. Process of brick making, therefore, involves selection of right type of raw materials, particle size dis-
tribution, mixing, compaction and heat treatment to develop strength.

2. Raw Materials

2.1 Magnesia
For manufacturing of magnesia carbon (MgO-C) bricks, high purity synthetic dead burnt magnesia produced from
seawater magnesia (MgO) was mainly used. However, with the availability of fused natural magnesia from China at
competitive price, most of the seawater magnesia plants of the world have stopped production. Japan was one of the
major producers of seawater magnesia and the country had 6 companies, which produced 6.88 million tons in 1974
from their 9 plants1. After 1995 only one company is operating with only one plant and produced about 0.1MT in the
year 2000. On the other hand, world wide up to around 1980, several companies participated in the market of high
purity magnesia, and in 1981 the production capacity of synthetic magnesia reached a peak of more than 2 million
tons. However, similar to situations in Japan, after latter half of 1990s when Chinese fused magnesia had become a
standard grade in the world market, the production of seawater magnesia clinker for refractories tended to decrease.
The number of manufacturers decreased to 4 companies in European area, 3 in North American, 2 in Asia and 1 in
Near East, a total of 10 companies in 9 countries. Their total production capacity diminished to 1.15 million tons, but
the actual production was estimated to be around 0.75 million tons.
 Manish Kumar Kujur et. al. / Materials Today: Proceedings 5 (2018) 2359–2366 2361

China began to produce fused magnesia in the 1960’s, but the production and application of it had been very limited
until the emerging and development of Magnesia - carbon bricks in the early 1980’s worldwide. In 1999 China
exported 0.22 million tones of fused magnesia2. Many reputed refractory companies have also started manufacturing
magnesia carbon bricks in China.

Since 1991 Australia is producing naturally sourced different types of Magnesia like Magnesite, Calcined, Sintered
and Electro fused magnesia. Today, both fused natural magnesia and sea water magnesia are used for manufacturing
of MgO-C bricks.

The MgO content of magnesia raw material is not in itself the major characteristic controlling the properties and
performance of the refractory product. The type, quantity and relative proportions of the chemical impurities present
in the magnesia have a fundamental effect on the slag resistance and high temperature mechanical properties.

Major impurities present in magnesia are SiO2, CaO, Al2O3 and Fe2O3. B2O3 is normally not present in natural
magnesia but it is the most harmful impurity present in seawater magnesia. It is to be restricted below 0.03%. Effect
of these impurities on high temperature strength has been reported in great detail by Gilpin and Spencer 3. Al2O3 is
more harmful compared to Fe2O3. While harmful effect of SiO2 can be controlled by proper lime silica molar ratio.
Poirier et al 4 conducted wear measurement in converter and reported that MgO% in magnesia is important up to
certain level while higher crystal size is more beneficial for lower wear rate. Crystal size can be increased to some
extent by high temperature sintering and to a great extent by fusion. Fig.1 shows crystals of sea water magnesia and
fused magnesia, effect of mixing fused magnesia (up to 50%) with sintered magnesia on slag corrosion was studied
by Horio et al 5. Wear rate reduced with the increase of fused magnesia content in contact with low basicity slag
having basicity of 1 and 2 while FeO were 10 and 30% respectively Matsui et al 6 reported that fused magnesia is
advantageous over sintered magnesia when MgO concentration of slag is nearly saturated and chemical reaction is
hard to initiate and the basicity of slag is high and slag penetration tends to occur through grain boundaries.

Dead Burnt Magnesia Natural magnesia Sea water magnesia Fused Magnesia
(Ned-MAG) (Q-MAG) (SWM) (FM)
Fig. 1. Microstructure of different types of Magnesia

2.2 Seawater Magnesia

For manufacturing of magnesia carbon bricks, high purity synthetic dead burnt magnesia produced from sea water is
mainly used. Sea water contains about 1.3gm of Mg +2 per litre of water which is equivalent to 0.2% of MgO 1. High
purity lime or dolomite is used for precipitation of Mg +2 to Mg(OH)2 . In 1936, Chesny developed an industrial
process for production of magnesium hydroxide and his method was not very much different in principle from the
process practiced at present. The conditions for obtaining good quality magnesium hydroxide are described in the
following: i) Removal of impurities from lime stone, ii) Removal of impurities and carbonate components in sea
water, iii) Improvement of the decomposition and filtration capabilities of the precipitated magnesium hydroxide.
Chemical and physical properties of sea water magnesia are given in Table-1
 2362 Manish Kumar Kujur et. al. / Materials Today: Proceedings 5 (2018) 2359–2366

Table – 1 Chemical and physical properties of sea water magnesia

Properties I II III
Chemical Analysis (%)
MgO, min 97.0 97.0 99.0
CaO ,max. 2.0 2.0 0.80
SiO2 ,max. 0.35 0.35 0.05
Fe2O3 ,max. 0.20 0.20 0.07
Al2O3 ,max 0.12 0.12 0.05
B2O3 ,max 0.03 0.03 50ppm
Bulk density (g/cm3), min 3.40 3.40 3.42
Avg. crystal size (micron), min 100 140 60-70
2.3 Fused Magnesia
Besides sea water magnesia fused natural magnesia from China is increasingly being used by different refractory
manufacturers for both economic and performance point of view. In China, fused magnesia is produced in three-
phase electric arc furnace 7. Although there are several hundred fusion furnaces in China, the devices and process
are similar: 1,200mm in upper diameter, 1,400mm in height, power transformer between 400 – 800 kVA, voltage
100V and current- 500A. Taking super grade magnesite or calcined magnesite as the raw materials, 12 hours is
needed for a cycle. The energy consumption is about 4,000 kWh/10T. There are also some jumbo furnaces in
China with power transformer 1200-1800 KVA. The size of furnace reaches 1600mm diameter and 2200mm in
height, 16 hours each cycle. China specifies four classes of fused magnesia according to their physical and chemical
properties. The chemical composition and physical properties of this fused magnesia are given in Table 2.
Table 2: Chemical and physical properties of standard fused magnesia 8
Class MgO(%), SiO2(%), CaO(%), Bulk density
min max max (g/cc), min.
DMS-98 98.0 0.6 1.2 3.05
DMS-97.5 97.5 1.0 1.4 3.45
DMS-97 97.0 1.5 1.5 3.45
DMS-96 96.0 2.2 2.0 3.45
2.4 Graphite
Since the carbon component of MgO-C brick has a dominating effect on many brick properties, the nature of the
carbon needs to be discussed. The premium quality products invariably contain flake graphite, and not "amorphous"
carbon. Flake graphite particles resemble a flat plate and are distinguished by a high degree of crystallinity that
gives it a better thermal conductivity and oxidation resistance than other forms of carbon. This particular property
enhances the spalling characteristics of MgO-C composite. Typical properties of different qualities of graphite are
given in Table 3.
Table – 3 Properties of graphite used
Properties Regular Higher purity Very high purity
Fixed Carbon 95 min 96 min 98 min
Ash 5 max 4 max 2 max
Volatile matter 0.5 max 0.5 max 0.5 max
Moisture 0.5 max 0.5 max 0.5 max
Sakaguchi et al 9 studied the effect of graphite particle size of resin bonded MgO-C bricks. Three types of graphite
particles of size <1mm, <0.15mm and <0.03mm were used. They observed that porosity; bulk density and crushing
strength are not much affected by the particle size of graphite but values of modulus of elasticity and permeability
decrease with a decrease of particle size of graphite. On heat treatment at 1000oC or 1500oC in coke, they found that
modulus of rupture of specimens was reduced and the effect was more pronounced with increase in particle size of
graphite. They also found that in case of specimens containing graphite with large particle size, spalling resistance
 Manish Kumar Kujur et. al. / Materials Today: Proceedings 5 (2018) 2359–2366 2363

improved. On the other hand, use of fine graphite resulted in dense brick texture, which retarded chemical reactions
and thus improved oxidation-abrasion and corrosion resistance.

Horio et al 5 conducted corrosion test in high frequency induction furnace at 1700± 25oC and found that higher the
graphite purity, more remarkable is the improvement in the corrosion resistance. Significant improvement of
corrosion resistance was observed when graphite purity increased from 95 to 98% (Table 3 & Fig.2). Naruse 10
reported that with graphite of 0.7, 3.6 and 7.9% ash content, corrosion index were 72, 80 and 100 respectively when
tested with a slag having CaO/SiO2 of 3.3 and total Fe of 13.3%.
Table – 3 Slag test with different purity of Graphite
Sample Nos With 10% graphite Corrosion Index
(Av. of samples)
3,5 & 10 3 % Ash 82
1&6 5 % ash 100
8,4 & 9 12 % ash 113
2&7 20 % ash 130

Fig. 2. Magnesia Carbon brick samples after rotary slag test with different purity of Graphite
2.5 Binder
For manufacturing of magnesia carbon bricks, liquid phenol formaldehyde resin or pitch is used as binding material.
Resin, being liquid at room temperature, has the advantages of mixing and pressing at ambient temperature. But
pitch is solid at ambient temperature and therefore elaborate melting, storage and handling facilities are required for
pitch handling. Moreover, it requires high temperature mixing and pressing. But the advantages of pitch bonding are
that it is much cheaper than resin. Carbon generated after pyrolysis of pitch is graphitizable whereas carbon
generated from resin is amorphous which is less resistant to oxidation and requires antioxidant. Also the weight loss
of pitch-bonded brick is slower at 1000oC as compared to resin. Resin is thermosetting in nature and the bricks after
curing are generally brittle in nature. Pitch is thermoplastic in nature. It melts on heating and then after
polymerisation, it becomes hard and brittle. During heat treatment (curing) of MgO-C bricks pitch is partly
polymerized and therefore during use it is expected to absorb stresses and reduce the brittle nature of only resin
bonded bricks.

Phenolic resins can be roughly classified 11 into two groups, resol and novolac. Ethylene glycol is mainly utilized as
solvent for production of resol and novolac type of resins in liquid state. In solid state novolac type resin are mainly
utilized as powder form. Resol resin has lower shelf life (1-1.5 month) as compared to novolac resin (shelf life
6months), which requires catalyst for setting.

Tar and pitch find application as binders in the field of refractories for both dolomite and magnesite blocks used in
oxygen steel making converters. The dividing line between tar and pitch is fairly arbitrary. In UK a pitch has a sof-
tening point above 45oC (R&B) and a tar softens below that temperature 12. The major source of crude tar is by-
product from carbonization of coal in coke ovens making metallurgical coke.
2364 Manish Kumar Kujur et. al. / Materials Today: Proceedings 5 (2018) 2359–2366

However, pitch or resin looses about 50% weight after carbonization and therefore, use of higher amount of these
binders will generate higher porosity after coking. It is therefore necessary to use optimum quantity of these binders.

2.6 Antioxidants
Metallic powders are generally added to MgO-C bricks in order to suppress the oxidation of carbon to become
important components. There are many reports concerning the behavior of metal, and their suppression effects on
oxidation of carbon. Watanabe et al 13 studied effect of different metal additives (Al, Al-Mg, Ca-Si-Mg and Ca-Si-
Mg+Al) on strength after heat treatment at different temperatures in CO atmosphere. Strength (MOR) decreases with
increase of treatment temperature for samples without metal addition. In case of metal added sample strength reaches
a minimum at 600oC and then rises along with temperature rise, reaching a peak at 1000oC. Above 1000oC strength
tends to decrease.

Taffin et al 14 concluded that improvement in mechanical strength by addition of aluminium occurs when there is a
contact between the zones of influence, which leads to the formation of a honeycomb structure. Toritani et al 15
conducted rotary slag corrosion test at 1750oC for 1hr with a slag having 18% total Fe and CaO/SiO2 ratio of 1 and
indicated that with addition of Al, corrosion index was less (80) as compared to sample with Si (120) and without
metal (100). But when the cold face was insulated the result was different. Sample without metal addition showed
lowest corrosion index (120) as compared to Al (130) and Si (215) added sample. Ichikawa et al 16 studied the
oxidation behavior of MgO-C brick in actual furnace and found that Al addition was effective on gas oxidation.

3. Brick Making

Magnesia-carbon refractory essentially constitute of magnesia grains and natural graphite. In order to make a
compact or brick from these materials, liquid phenol formaldehyde resin is generally used, which acts as binding
material at room temperature. At higher temperature, carbon network produced from resin provides necessary
binding.
The fabrication of this material involves preparation of batch with optimum particle size distribution, mixing of the
two main components in particulate form with liquid binder, compaction under optimum pressure to get optimum
bulk density and heat treatment (curing) to develop reasonably high strength.

In powder compaction, selecting the correct distribution of sizes is of greatest significance in minimizing the
porosity. Whilst it is known that a wide distribution of particle size is required for compaction of isometric particles
to low porosity, the precise distribution depends on the range of particle size to be allowed in the powder (i.e. on the
maximum size) and it is usually determined by trial and error.

MgO-C bricks containing different amount of graphite are used in steel plants. Generally maximum amount of
carbon used in these bricks is 20-22%. Depending upon the graphite content, physico-chemical properties of these
composite varies widely. Magnesia and flake graphite displays grossly different morphology with oxide particles
often being isometric while the flake may show aspect ratio of 60 or so. Therefore, packing behavior of graphite is
different than magnesia particles and same grading is not suitable for getting maximum density. Detailed studies
have been conducted 17 by using the following equation of Andreasen 18:
y = 100 (d/D) n
Where
y = % (weight) of material of size less than d
D = maximum particle size
n = an empirical parameter.
Optimum `n' values for distribution of MgO particles for different graphite level are as follows:
Graphite % 0 3 5 10 15 20
n 0.4 0.4 0.5 0.7 0.7-0.8 0.8-1.0
 Manish Kumar Kujur et. al. / Materials Today: Proceedings 5 (2018) 2359–2366 2365

It has also been found 17 that maximum bulk density was obtained with 5% graphite while porosity decreased with
increase in graphite content. Drop in porosity is sharp up to 10% and then gradually decreased up to 15%. With
further increase in graphite to 20% the porosity has dropped marginally. Lowering of porosity with increase in
graphite content indicates that packing efficiency improves with addition of graphite up to certain level. Cold
crushing strength values decreased with the increase in graphite content.

Mixing is done in high intensity mixer. Pitch bonded bricks are mixed at about 130oC while resin bonded bricks are
mixed at ambient temperature. Metal powder(s), catalyst (for novolac type PF resin), pitch powder and a part of
microfines are premixed in dry condition and kept separately. Coarse fractions are first charged into the mixer and
liquid binder is gradually added to get uniform coating. Then graphite is charged and mixed for some time. Finally
fines along with premixed materials are added and the mixer is rotated for sufficient time to get perfect mix suitable
for pressing.

Pitch bonded bricks are pressed in hot condition to get maximum compaction. But resin bonded mix is stored for 12-
36 hrs before pressing and the process is known as aging. Resol bonded mix requires higher 24-36 hrs aging time
depending upon the ambient temperature and season. Novolac type PF resin requires less aging time compared to
resol type resin. Improper aging leads to lamination while excessive aging reduces bulk density and increases
porosity of the brick. Pressing at high pressure improves bulk density. Product quality further improves with vacuum
pressing. Bricks are generally pressed at specific pressure of 2000 kg/cm2

In order to develop strength, resin bonded compacts are heat treated at low temperature for certain time and the
process is known as curing. Curing temperature ranges from 110 to 300oC for duration of 10 to 24 hrs as reported by
different brick manufacturers. During curing process, initially excess phenol or formaldehyde as the case may be for
resol or novolac; evaporates and then water molecules produced due to condensation reaction leaves the matrix. If
samples are cured directly at higher temperature then the surface gets hardened within a few minutes as it gets heated
first and then as the interior is heated, volatile matter gets entrapped forming porous and weak structure. It is
therefore necessary to cure the blocks at lower temperature for reasonable holding time. Similarly pitch bonded
bricks are heat treated at 200-300oC for uniform distribution of pitch and to avoid the danger of slumping during use.

4. Application in Steel ladle (Metallurgical container)

Although basic refractories like MgO-C have very good high temperature properties including very high slag
corrosion resistance, they have high thermal expansion coefficient and thermal conductivity as compared to other
refractories. Thermal conductivity is dependant on carbon content and also type of bonding. Thermal conductivity of
3% graphite containing pitch bonded brick is ~7W/m.K while that of 15% Graphite containing pitch bonded brick is
~13w/m.K. The same for 20% graphite containing resin bonded brick varies from 9 to16 at the temperature of 200-
1000oC. These aspects are to be taken care during lining by providing suitable insulation and lining design.

The thermal and metallurgical load in steel ladles is not uniform in all areas of the ladle and this leads to uneven
erosion in different zones of ladle lining. Ladles have 4 zones such as bottom, metal zone, slag zone and free board
area and generally preferential erosion takes place in slag zone and bottom impact areas. Concept of zonal lining has
therefore been adopted using different quality brick to have uniform erosion and higher life. At present steel ladles
lining life of more than 100heats are now being achieved by many Indian steel plants. However, this life has been
achieved after changing or repairing slag zone, bottom well block and seating block. All these repair work needs
cooling of ladles and further preheating before coming to operation. This reduces availability and hampers
production. Future directions are aiming towards achieving maximum straight ladle life by improvement of brick
quality of weaker areas and improving operational refractories.
2366 Manish Kumar Kujur et. al. / Materials Today: Proceedings 5 (2018) 2359–2366

5. Future developments in Magnesia carbon

In the field of MgO-C refractories, lot of developments has already been taken. In raw material front, purity of
magnesia and graphite has reached to its maximum. Use of single bricks formed under very high pressure, use of
different special additives for binding strength, use of different types of antioxidant for protection of graphite etc
have been well established and are being practiced by most of the plants. However, new developments are likely in
the following direction.

5.1 Incorporation of spinel bricks

In recent years alumina magnesia spinel bricks are being used in bottom and metal zones of steel ladles to achieve
higher lining life. With repeated repairs, lining life can be extended to double the life of MgO-C bricks. MgO.Al2O3
(spinel) present in this lining plays a key role to prevent slag attack. Spinel contains lot of interstitial vacant
octahedral and tetrahedral sites and is considered to prevent slag corrosion by absorbing large amount of bivalent
and trivalent elements (Mn++, Fe++ , Fe3+, Cr3+) from slag. Slag thus become silica rich, highly viscous and form a
protective layer over refractory surface. Whereas MgO-C refractories are widely used in BOF and steel ladles due to
their superior properties in respect of spalling resistance, corrosion resistance and high temperature mechanical
properties. Suitable incorporation of spinel may be beneficial for improving ladle life. These types of bricks are
being used extensively for the production of ultra low carbon steel as the bricks contain little or no carbon.

5.2 Lower thermal conductivity

Thermal conductivity of MgO-C brick is high due to use of higher percentage of graphite. Higher amount of carbon
is used to achieve high thermal shock resistance and lower slag corrosion. Recent works are directed to achieve
higher slag corrosion resistance at lower carbon level to get lower thermal conductivity but without sacrificing
thermal shock resistance. With the incorporation of nano carbon particles, MgO-C having high slag corrosion
resistance and thermal spalling resistance similar to higher carbon containing conventional brick could be developed
with low carbon.

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