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Carbon Based Refractories

Article  in  Journal of the Ceramic Society of Japan · October 2004

DOI: 10.2109/jcersj.112.517

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 Review
Journal of the Ceramic Society of Japan 112 [10] 517–532 (2004)

Carbon Based Refractories

J[{“ÜLÏΨÌTv
Emad Mohamed M. EWAIS
Refractory & Ceramic Materials Lab., Central Metallurgical R & D Institute (CMRDI ), P.O. BOX 87Helwan, 11421Cairo, Egypt

Carbon based or containing refractories has been attracting great attention because of their unique properties
e.g. high thermal conductivity, low thermal expansion, high resistance to thermal shock and chemical inertness
to the slag. They are classified into two groups; carbon/bricks/blocks and carbon containing materials. Carbon
containing materials are further classified into carbon containing basic refractories and non­basic refractories.
Manufacturing processes are considered. The properties e.g. physical, thermal, mechanical and chemical are
reviewed. Antioxidant and bonding materials for these types of the refractory products are reviewed. Their appli­
cations are also considered. [Received April 26, 2004; Accepted July 30, 2004]

Key­words : Refractories, Carbon, Graphite, Magnesia, Dolomite, Alumina, Zirconia, Manufacturing, Antiox­
idants, Bonding, Physical, Thermal, Chemical, Mechanical, Application

1. Introduction and with increasing frequency, these elements are used in

Refractories are materials (usually nonmetallic) that main­ combination with carbon, Fig. 1.9) Carbon or graphite refrac­
tain sufficient physical and chemical stability identity to be tories are also used with carbon as the sole constituent in the
used for structural purposes in high temperature environments form of blocks or bricks.
encountered in the process industries. While refractories It is well known that the major refractories production is
are always exposed to high temperatures, the effect of other associated with the steel industry, i.e. if steel production
environmental conditions play a significant role in the perfor­ increases, refractories production also increases, and vice
mance of refractories during service. These include: mechani­ versa.10),11) Recently, a dramatic reduction of refractory
cal stresses, thermal cycling and associated stresses, erosion consumption per ton of steel has been achieved in the iron and
and corrosion by hot gases and such molten materials as steelmaking industries. This is attributed to improve opera­
metals, slags, or glasses. Today, refractories are absolutely tions specifically in process control and hot gunning repair. It
essential to industry. Without refractories, few manufacturing also results from the development of continuous casting
processes could be carried out.1) The production of metals, processes. The quality of refractories, specifically carbon
cement, glass, petroleum products, and much of our electrical containing or based refractories, truly advanced composite
energy depends on refractories. Yet, few people know relative­ materials, also played an important role in achieving reduction
ly what refractories are or realize their importance, because in refractory consumptions (See Table 1).12),13)
these materials seldom come to the attention of the general
public. Refractories are usually sent directly from their point
of manufacture to another factory, where they are used to
make consumer items that bear no trace of the refractories
that were essential for their production. In addition to the
category of refractories characterized by large­scale used in
the process industries, there are others that are used for
more specific applications. For example, in the aerospace
industry extremely high temperatures are encountered from
propulsion systems and friction heating at high velocities in
the atmosphere. There are also applications in the field of
nuclear energy. Such applications that may require the
massive use of refractories are a vital factor in the success of a
particular system.
Refractories are classified primarily on the basis of their
chemical composition and the forms in which they are
used.2)–8) To a lesser extent, refractories may be identified by Fig. 1. Base material pyramid with the location of the refractory
materials.
association with a particular function such as thermal insula­
tion, or a special manufacturing process such as fusion cast­
ing. Although the types of refractories manufactured for the
industrial use are vast, it should be recognized that only few Table 1. Refractory Consumption by the Steel Industry Worldwide
chemical elements form refractory compounds are available in
sufficient quantities to be used economically. The preponder­
ance of allgheavyhrefractories are manufactured from com­
pounds that involve the elements: silicon, aluminum, magnesi­
um, calcium, chromium, and zirconium. The oxides of these
elements are singly used or in various combinations. Recently
517
 518 Carbon Based Refractories
In summary, there are many types of refractories. Carbon
containing or based refractories are a class of refractories
according to chemical composition classification. Because of
the progress in this class and its application to iron and steel­
making processes, the refractories containing or based upon
carbon (carbon bricks/blocks, carbon containing basic refrac­
tories, carbon containing non­basic refractories) are reviewed
in the light of these processes.
2. Carbon and graphite refractories
Elemental carbon is found in nature in the form of dia­
monds, graphite and above all as coal. For refractory pur­
poses natural and artificial graphite (coke from coking
plants) are important for the manufacture of carbon bricks.
The raw materials for carbon blocks should have ash content
as low as possible as well as a high yield.14)
Because carbon or graphite refractories are both made up of
the single element carbon, their distinction depends upon the
basis of their crystal structure. Carbon refractories generally
do not have a well­ordered crystalline structure and may be
considered amorphous, depending on the initial raw materials
and the temperature that reached during the manufacturing.
The graphite structure is well known,15)–17) Fig. 2 and indi­
cates a planar structure with an infinite two dimensional array
of carbon atoms arranged in hexagonal networks in the form
of a giant aromatic molecule. The carbon­carbon bond (cova­
lent) in the plane is strong as indicated by the interatomic
distance of 0.142 nm where the bonding (van der Waal type)
between the planes is weak the interatomic planar spacing
being 0.304 nm. Consequently, graphite has a layered struc­
ture and may occur in flakes or show preferred orientation of
its crystallites because of the alignment of the crystallites
in fabrication process i.e. the planar structure results has
anisotropic properties.
The properties of graphite, in particular single crystal
graphite, in terms of thermal expansion, thermal conductivity
and compressibility are attributed to the structure.16),18)
Thermal expansion perpendicular to the planes is 200 times
that parallel to the planes. Thermal conductivity paralleled
to the planes is 200 times that perpendicular to the planes.
Its compressibility is 104–105 times greater in the direction
perpendicular to the plane. However, the degree of anisotropy
decreases for the graphite components produced from a
random array of graphite crystallites and the properties of
such a body can't be readily inferred from orientation factors
in the random structure. This is the case for manufactured
carbon refractories as they contain amorphous carbon and/or
well ordered crystalline structure.
Interesting properties for this refractory class in terms of
Fig. 2. Crystal structure of graphite.
distribution of size pore, low porosity, low thermal expansion
and zero permanent linear change at 1600‹ C, were reported, in
particular, if this type is manufactured from anthracite cal­
cined at very high temperatures(1600–1800‹ C), extruded, im­
pregnated. This improvement in the properties was based on
the well distribution of the grain size and, in turn, minimizing
the intergranular spacing of the product.19),20)
Three groups of refractory bricks out of carbon have been
reported: amorphous, part­graphite or semi­graphite and
graphite bricks. In recent years two further types designated as
gmicroporoushwere developed from the first two groups by
additions of additives to improve their wear resistance.20)
2.1 Manufacturing
Carbon and graphite refractories are naturally occurring
graphite, coal, petroleum coke, coal­tar pitch, artificial
graphite, coke from mines, gas­calcined anthracite and electri­
cally calcined anthracite.21) Tar­pitches, petroleum pitches
and other organic materials are used as binders. The raw
materials are prepared, ground, sieved, classified, mixed to
batches depending on the desired property values, heated to
approximately 160‹ C depending on the type of bond, and
mixed with binder to get the so­calledggreen batchhorggreen
mixture.hNext the mix is shaped. Vacuum vibration equip­
ment, die presses, extrusion presses, isostatic presses and
ramming equipment are used to form the batch/mixture into
the desired shape. After shaping the so­calledggreenhshape is
subjected to a firing process up to approx. 1200‹ C. The binder
converts to coke. It is possible to accomplish subsequent
densification and compaction by impregnating the blocks with
impregnation agents, which are similar to the binders with
regard to their composition. The impregnation agent, which
has entered the pores, is also converted to coke during further
firing'.20)–22)
2.2 Physico­chemical properties
Carbon and graphite are not wet by most molten materials
because of the low interfacial tension between carbon or
graphite and molten materials. They have excellent thermal
shock resistance, and their strength increase when they are
heated. At 2500‹ C, the tensile strength of graphite is roughly
twice as great as its room temperature tensile strength, which
is approximately 2000 psi.1) Carbon and graphite have a
range from good to superb electric conductivity, thermal
conductivity and low expansion coefficients. Their thermal
shock resistance are sufficient for standard applications.
Despite good thermal conductivity and thermal shock resis­
tance the application of carbon blocks is restricted because
they are susceptible to be attacked by oxygen, steam and CO2
in an oxidizing atmosphere above 400‹ C.
The wear mechanisms for carbon bricks lining the hearth
and hearth wall of blast furnace were reported.23) Six wear
mechanisms are responsible for the damage of carbon bricks;
1) the dissolution of carbon in pig iron.24) 2) the pick­up of
potassium oxide and migration of it into the brick to tempera­
ture zones of 900‹ C and reaction with the crystalline phases of
carbon e.g. mullite, a­crystoballite and a­quartz under the
formation of kalsilite (K2OEAl2O3E2SiO2 ) and leucite (K2OE
Al2O3E4SiO2 ).25) These reactions are combined with a volume
increase, which causes a destruction of the brick texture.
Further pick­up of potassium and the formation of potassium­
carbon compounds of the formula C8K, C24K and C60K causes
a swelling of the carbon bricks and a complete disintegration
of it. 3) MnO pick­up of the brick and its reaction with ash
compounds at temperature above 1200‹ C forming manganese
aluminium silicates. This in turn reduces the modulus of
rupture of the brick. 4) the reaction of picked­up ZnO with
 Emad Mohamed M. EWAIS Journal of the Ceramic Society of Japan
binding phases of the carbon bricks destroying it, formation
of zinc orthosilicate (2ZnOESiO2 ) or zinc aluminate during
shut down of the blast furnace.25) 5) oxidation of carbon by
water vapor26),27) 6) thermal stress due to the existing pressure
within the lining.24)
2.3 Applications
Because their properties, graphite and carbon refractories
are serious contenders for applications in a reducing environ­
ment. Blast furnaces use appreciable quantities of carbon and
graphite, particularly in the hearth, but carbon and graphite
may also find application in the bosh and other places such as
tapholes.28)
With water­cooled shells, cupolas have been lined with
carbon in the wells. Because of its high electrical conductivity,
graphite is used for electrodes in electric furnaces to generates
the arc. Because graphite can be easily machined, complicated
shapes can be cut from stock in the form o bars, slabs, or
cylinders. In order to accomplish the reduction process at
electric arc temperature for the production of Si, FeSi,
FeMn ...etc., carbon electrodes with various graphite addi­
tives are applied. In these furnaces the bottoms are partially
lined with carbon blocks.
Carbon bricks are also installed as lining in tanks for
making phosphoric acid because carbon has a very good
resistance to acids. Wear resistant graphite plates are used as
shaped bricks for the manufacture of fused cast corundum
bricks.
It must be mentioned that there is no international standard
for carbon and graphite refractories and properties depend
only on the manufacturer according to the request of con­
sumer.
3. Carbon containing materials
Graphite and carbon also are used in combination with
other refractory materials to form a composite suitable for
certain applications. The importance of carbon additions can
be seen in the wear reduction by reducing infiltration depth
and in the bond of the unfired bricks. In addition, thermal
shock resistance is improved by increasing thermal conductivi­
ty and decreasing thermal expansion.29)
The brick bond of unfired products in a coked operation
state is based on the adhesion between the coke lattice and
refractory particles as well as on the adhesion within the coke
lattice with partial direct atomic bonds, secondary valence
bonds and van der Waal forces.
The infiltration depth is changed substantially by carbon
from centimeters to millimeters. Consequently, the wear
mechanism of the bricks is changed drastically. Two factors
are responsible for this:–
(1) The reduction of iron oxide in the liquid infiltration
by metal. The eutectic temperature of the infiltrate is increased
to its solidification point (with CaO/SiO2 molar„2 if in­
filtrate contains FeO).
(2) Non­wetting between the oxide infiltrate and carbon
of the brick at a contact angle f„90‹(with CaO/SiO2 molar
ƒ2 if infiltrate doesn't contain FeO).
In addition to the FeO content, the CaO/SiO2 molar ratio is
a decisive in determining which of the two effects take place.
The CaO/SiO2 molar ratio regulates itself on the hot face side
directly in the front of the carbon­containing brick zone. With
magnesia and magnesia­doloma brick, the CaO/SiO2 molar
ratio always stays„2 because of the high CaO content in the
brick. Consequently, the reducing effect is always active with
these bricks if the slags contain FeO. For magnesia bricks,
however, this ratio can drop belowƒ2 as a result of the differ­
112 [10] 2004 519
ent precipitation during infiltration. The iron ions of the
infiltrate are absorbed by the periclase (MgO in accordance
with the chemical balance within the solution). Consequently,
the melt losses iron before it reaches the carbon in the brick.
Due to the CaO/SiO2 molar ratio droppingƒ2, the infiltrate
remains liquid and agile despite its loss of iron. In this case,
the non­wetting effect prevails. The same applies for slags
without FeO.
The decisive factor for effective utilization and application
of C­containing bricks is the burnout speed of carbon. In pitch
or resin­bonded bricks, a cracked carbon lattice forms the
brick bond. This means that carbon burnout leads to a
decisive bond loss. Consequently, C­containing bricks can
and should be used where reducing gases, that is a furnace
atmosphere with low oxygen partial pressure, are predo­
minant. Examples are converters, electric arc furnaces or the
metallurgical ladle. In order to lower speed, additives for
retarding oxidation are also used.
Carbon containing materials are divided into carbon based
basic refractories and carbon based non basic refractories.
Each type also can be classified according to the binders used.
This means that the carbon to refractories carry out via differ­
ent techniques to manufacture these types.
3.1 Manufacturing
The bricks or the blocks of these types of refractories are
manufactured by grinding the raw materials, sieving, classifi­
cation, mixing to batches depending on the desired proper­
ty values, heating to approximately 100–200‹ C depending on
the type of bond, and mixing with binder to get the so­called
ggreen batchh or ggreen mixture.h However, the bricks
bonded with synthetic resin are manufactured cold or hotƒ
100‹ C with liquid and a hardener. Next the mix is shaped.
Vacuum vibration equipment, die presses, extrusion presses,
isostatic presses, hot pressing and tempering, and ramming
equipment are used to form the batch/mixture into the desired
shape. After shaping, the so­calledggreenhshape is subjected
to a firing process up to approx. 1200‹ C. The binder converts
to coke. It is possible to accomplish subsequent densification
and compaction. It is possible to accomplish subsequent den­
sification and compaction by impregnating the blocks with
impregnation agents, which are similar to the binder in regard
to their compaction. The impregnation agent, which has
entered the pores, is also converted to coke during further
firing cycle.
3.2 Bonding materials
The binding materials for carbon based refractory materials
should have an ash content as low as possible as well as a high
yield. Tars, coal­tars or coal­tar pitches are the commonest
types of materials used as carbon sources and binders for
refractory bricks. They have long been used in practice. The
physical properties of the tar or pitch influence the processing
behavior greatly during manufacture. Conversely, the choice
of binder is also determined by the particular processes in
use.30) The softening point of the residual binder should not be
exceeded prior to carbonization for any given bricks to
prevent spalling.31)
Because of the potential health hazards in the handling of
such materials and the evolution of hazardouds pyrolysis
products, there is a tendency to use polymers to replace tars,
coal tars and coal­tar pitches.32)–35) Phenolic resins, both
novalacks and resols are favored because they are or can
become thermosetting and because they can be pyrolysed
during coking to achieve a high carbon yield. In addition to
favorable pyrolysis and carbonization behavior, they are
available in various forms, such as solutions, powder resins,
 520 Carbon Based Refractories
solid materials, and melts. They also serve as binders and
impregnating agents for carbonaceous materials and refracto­
ry products. Synthetic resin bonded bricks offer the following
basic advantages:36),37)
(1) Their production and processing is environmentally
acceptable.
(2) Their production by means of the cold mixing method
conserve energy.
(3) The products can be processed in uncured conditions.
(4) The products have no plastic phase when heated up, in
contrast to tar­pitch binders.
(5) The carbon content (more graphite or soot) can
increased to augment resistance to abrasion and slag attack.
The control in cure of the resins is very important factor
where some resins tend to harden in a comparatively short
time. This, in turn, reduces the time that mix can be retained
before it must be shaped into bricks or other desired shapes.
Lyer and Shah38) contributed in solving this problem by
control in pH in the presence of a catalyst.
During heating of this product in the operation state, the
pitch form elementary carbon (coking) at 300–600‹ C by
pyrolysis in liquid state leading to a separation of the volatile
constituents (cracking).29) Laminated carbon packages form
with good structure at the hexagonal base plane. These carbon
packages are easy to graphitize and possess good optical
anisotropy. However, in the c direction the carbon planes stay
shifted and twisted, with varying degree of distance, even at
the highest operation temperature. This intense degree of one­
dimensional imperfection corresponds to a polycrystalline
graphite lattice (the three­dimensional graphite structure is
not obtainable until„2000‹ C). In contrast to pitch, the
pyrolysis of phenolic resins, which are synthetic polyconden­
sation products occur in solid state. The strong space inter­
lacement of the molecule chains and, as consequence, missing
agility prevents an oriented deposit of hexagonal carbon
layers. A poorly arranged and strongly interlaced lattic is the
result. This prevents gliding and cleavage. Therefore, these
cokes are hard and very sensitive to oxidation due to the large
inner surface.39)
Phenolic resin has been widely used for its excellence knead­
ing properties, molding properties and economy for carbon
containing bricks. Although this binder has superior proper­
ties but it has some drawbacks. Firstly, a phenolic resin gener­
ates gases such as water, hydrogen, ethylene, phenol, cresol
and xylenol when carbonized in temperature range of from
350–650‹ C causing air pollution and odor, etc.40)–42) Secondly,
where a phenolic resin is used as a binder, the resulting struc­
ture is dense and has insufficient open cells. Therefore, the
structure is liable to destruction due to the evolution of
decomposition gas on heating. Thirdly, carbon produced from
a phenolic resin is a glassy carbon inferior in resistance to
spalling. Although the phenolic resin has a high residual car­
bon on burning, the resulting products have poor spalling
resistance. Yamamura et al.43) proposed the using saccharified
starch of a non­aromatic organic high­molecular compound to
overcome the disadvantages of the pitch­bonded type and
using of a hexahydric alcohol as well as the first to the third
drawbacks associating the use of a phenolic resin.
3.3 Carbon­containing basic materials
3.3.1 Carbon containing magnesia refractories
The evolution and use of magnesia refractories in combina­
tion with carbon started over forty years ago, in the early
1950's, with pitch bonded dolomite refractories, developed
primarily for the basic oxygen furnace. In these early days,
some of these linings in the basic oxygen furnace lasted only
100 heats, often not giving sufficient time to reline the se­
cond vessel in a two furnace shop.44)
Very measurable improvement came when magnesia fines
were used in conjunction with the dolomite coarse fractions
bonded with pitch. Further improvements came with the all
magnesia pitch bonded brick. In the 1970's the burned and
impregnated magnesia brick with finite pore size became the
standard for the charge pad and other high wear areas, start­
ing the beginning of the zoned lining for basic oxygen
furnaces.45) About that time magnesia purity became a factor
and a special low boron 96÷ magnesia grain having a lime to
silica ratio of 2 to 3F1 was used extensively.
The 1980's saw the development of resin bonded magnesia­
graphite, first with higher carbon content and then with the
addition of antioxidants to preserve the carbon content.46),47)
Recently fused magnesia grain, sintered magnesia with
larger crystallite size, and very high purity sintered magnesia
were introduced to further improve the corrosion resistance.48)
In addition to conventional pitch and resin bonded and
burned and impregnated magnesia brick, the following three
types of magnesia carbon brick are available on the market.
«The first series contains regular sintered magnesia (97÷
Mg0) with medium quality graphite (95÷C).
«The second contains high purity sintered magnesia (99÷
Mg0) with high purity graphite (99÷C).
«The third contains high purity sintered magnesia with
high purity graphite plus antioxidants.
Magnesia carbon refractories are classified into three types
according to the carbon:–
(1) Fired carbon­containing magnesia bricks (ƒ2÷C),
(2) Carbon­bonded magnesia bricks (ƒ7÷C)49) and
(3) Carbon­bonded magnesia­carbon bricks („7÷C)50).
The third one of refractory type is best suited classify on the
light of binder to two types as following:–
(1) Bricks with pitch bonded (with max. 15÷C), partial­
ly with subsequent pitch impregnation under vacuum or
secondary for special cases with antioxidants, and,
(2) Bricks with synthetic resin bond up to 25÷C) often
with added antioxidants (Al, Si, AlSi, Mg, AlMg, B4C among
others in powder form).
3.3.1.1 Production technology
MgO–C bricks are manufactured from high purity MgO
clinker i.e. natural, sea water and electrofused magnesia as
well as flaky graphite with carbon content of 86–99÷, carbon
black whether thermal or furnace with a natural gas or oil
base, and coke binders whether pitch or synthetic resins for
unfired products. In these types, a high chemo­thermal stabili­
ty is required from magnesia in bricks containing carbon. This
means that a CaO/SiO2 molar ratio of magnesia should be„2
as well as possibly slight contents of B2O3 and SiO2 which
form melts; furthermore, little Al2O3 and Fe2O3. In addition,
periclase boundary surface should be a negligibly reactive due
to low apparent porosity and large crystals.51),52)
Fired carbon­containing magnesia bricks are manufactured
by placing the fired magnesia bricks under vacuum at 150–
200‹ C and impregnated with pitch or resins. In this process, it
is not possible to obtain more than 2÷ residual carbon.
Repeated impregnation along with intermediate coking or the
separation of carbon out of furfuryl alcohol, for example, to
increase the carbon content, have not proven to be economi­
cally feasible.
Concerning to the properties, these bricks only differ from
fired magnesia bricks in regard to infiltration­retarding effect
of carbon. This has a decisive influence on the wear behavior
but is hardly noticed when comparing test or inspection value.
 Emad Mohamed M. EWAIS Journal of the Ceramic Society of Japan 112 [10] 2004 521

Table 2. Properties of Carbon Containing Magnesia and Magnesia Carbon Bricks

Table 3. Thermo Mechanical Properties of Carbon Containing Magnesia and Magnesia Carbon Bricks

The bricks are distinguished by superb erosion resistance due
to the firing of the brick. However, the thermal shock
resistance is only moderate (See Tables 2 and 3).
Carbon­bonded magnesia brick (pitch impregnated) is
manufactured by mixing magnesia and pitch at 100–200‹ C,
these bricks are shaped while still warm and tempered at
250–350‹ C to obtain sufficient hot strength. In addition to
tempering and using pitch instead of tar for improving the
carbon bond, carbon black is added, dehydrogenation agents
are used and pitches impregnates under vacuum are further
step. Carbon black can be dispersed in pitch in such way that it
will greatly strengthen the coke bond. Dehydrogenation agents
such as sulfur also increase the output of carbon.
N.B. 1–Hard coal pitch has the best performance/cost relative
of all coked binders.
2–Phenolic resin is not only used as binder for magnesia­
carbon bricks
with„7÷C but also sometimes for magnesia bricks
above 5÷C.
Carbon­bonded magnesia carbon bricks are characterized
by residual carbon content of more than 7÷. The obtained
high content of residual carbon can't be reached even by addi­
tion of graphite.
Carbon­bonded magnesia carbon bricks with pitch bonded
are manufactured by hot pressing and tempering at 250–
350‹C. The bricks bonded with synthetic resin are manufac­
tured cold or hot at temperature less than 100‹ C with liquid
phenolic resol or phenolic novalac solutions and a hardener.
Next, the binders are hardened at 120–200‹ C. Due to interlac­
ing, this ensures formation of a highly molecular and non­
meltable resite lattice.
Carbon­bonded magnesia carbon bricks having high pro­
perties in respect of resistance to thermal, structural spalling,
slag resistance and thermal shock resistance, etc. It is
manufactured from 60–97÷ sintered magnesia of bulk
specific gravity about 3.4 and 3–40÷ carbonaceous materials
and a carbon bonding formative agent53) for applications in
the converter.
The effect of impurities in magnesia upon the reaction
between magnesia clinker and carbon was estimated by meas­
uring the weight loss of MgO specimen reacted with graphite
at 1500–1750‹ C.54),55) It was found that the reaction between
the MgO clinker and the carbon was affected by the chemical
composition of the clinker rather than by its crystal size.
 522 Carbon Based Refractories
Fig. 3. Densification parameter as a function of residual carbon.
Therefore, in high purity system, no difference in the reactivi­
ty of sintered and fused MgO with carbon was observed. B2O3
in the clinker accelerated the reaction considerably. This was
attributed to the formation of a liquid phase in the CaO–B2O3
system at high temperature, which promote mass transfer.
CaO in the clinker accelerated the reaction, whilst Al2O3
depressed it. Thermogravimetric studies of magnesia carbon
reactions at 1700‹ C emphasize that there is no influence on the
average crystal size and the bulk density of high pure magnesia
grade.56)
Cooper reviewed the use of graphite in the refractory
industry and concluded that the graphite nature's is unique
raw materials and alters and controls the properties of
refractories.57) Kenan rationalized the improving in the quality
of the magnesia graphite and consequently increasing their
service life by the change of the type of carbon used; from
carbon black to graphite and Sri Lankan graphite to flake
graphite.58) The size and the quality of the graphite added
contribute in the quality of the magnesia­carbon bonded
refractories. The experimental results reported shows that the
use of high purity graphite with large size has some merit.59)
The properties in terms of porosity and density of carbon­
bonded magnesia bricks were investigated by Mikami and
Martinet.60) The results (Fig. 3) showed that the density
declines by adding more increasing carbon has a lower specific
graphite than magnesia (2.24 against 3.56). The ignited
porosity increases naturally by adding more carbon because of
the space occupied by the carbon burnout on ignition. Sig­
nificantly, the coked porosity rises very little by increasing the
carbon level.
3.3.1.2 Thermal properties
The thermal expansion of magnesia­graphite decreased the
expansion of magnesia more than it would be expected on a
simple volume basis which likely to be related to the compres­
sive nature of the graphite bond. Landy et al.61) has demon­
strated the decreasing of thermal expansion of magnesia
graphite products with increasing graphite level.
Excellent thermal shock resistance of MgO–C products
containing graphite level greater than 10÷ and existing as
continuous matrix was found.62) These results were attributed
to:–
The ability of the compressible graphite matrix to absorb
the expansion of magnesia grains.
The probability that any cracks formed fail to propagate
because of the grain mismatch and consequent poor bonding
between graphite and magnesia.
With increasing the graphite content of MgO–C bricks,
thermal spalling resistance increases.63) However, the thermal
spalling decreases with increasing the metal content.64)
Fig. 4. Effect of graphite.
Ichikawa et al. reported that the thermal shock resistance
of the MgO–C bricks increases with using a pitch of low
softening temperature.65)
3.3.1.3 Mechanical properties
The mechanical properties of MgO–C bricks depend on the
content of graphite of MgO–C bricks. The maximum values of
bending strength, elastic modulus (Fig. 4)62) and fracture
toughness were obtained at 2–3 vol÷ expanded graphite and
at around 5 vol÷ flake graphite.66) Addition of carbon
reduces the elastic modulus due to the separation of particle.
However, the strength of the MgO–C bricks increases with
using a pitch of low softening temperature.65)
An improvement of the strength in terms of hot modulus of
rupture (HMOR) and oxidation resistance of MgO–C due to
the addition of Al, Al{Ca–Si, Al–Cr and Al–B4C were
reported.67)–69) B4C gave the best results. Such improvements
were explained in the light of formation of a dense MgO layer
due to the additives. Watanabe et al. stated70) that the strength
of MgO–C refractories with Al and Si antioxidant is increased
at room temperature 900‹ C and 1000‹ C due to the strengthen­
ing of the bond by formation of carbide leading to densifica­
tion of the brick. However, using of B4C and CaB6 increases
the strength at temperature of 900, but it decreases at 1400‹ C
due to a decrease in the bonding force in particular at high
temperatures.
3.3.1.4 Antioxidants
Oxidation is a common problem in magnesium oxide–car­
bon(MgO–C), which are used primarily in the slag phase in
ladles and converters. To combat this issue, antioxidants are
widely used by MgO–C brick manufacturers. Antioxidants
form CO gas and Mg vapor which act as a buffer in the pores
of the brick and form a dense spinel phase in the reaction zone
of the brick. The spinel phase stops the infiltration of the
liquid slag and thereby helps prevent corrosion. Numerous
studies conducted on the effect of metallic and boron­bearing
antioxidants have shown that the combinations of a metallic
and boron­bearing antioxidant generally have the best
resistance against oxidation and slag corrosion. One study in
particular examined the oxidation resistance of MgO–C bricks
with aluminum (Al), boron carbide (B4C), calcium carbide
(CaB6 ) and zirconium boride (ZrB2 ) additives and combina­
tions of those additives after a heat treatment in air.71) The
study revealed that the best results were achieved by combina­
tion of Al and B4C or CaB6 (see Fig. 5).71) The effect of Al
and alumina additions on oxidation rate of MgO–C refractory
has been investigated.72) The author concluded that the oxida­
tion of MgO–C refractory decreases with increase in Al con­
tent mainly due to the reducing effect of the remained Al4C3
on PO at the oxidation reaction interface. However, alumina
2
addition increases the oxidation rate due to the slight increase
in apparent porosity.
 Emad Mohamed M. EWAIS Journal of the Ceramic Society of Japan 112 [10] 2004 523

Fig. 6. Liquid aluminum escaping from the alumina shell at 700‹

C
Fig. 5. Ratio of the area of the original to the oxidized material of (left image) and formation of aluminum carbide at 700‹ C(right
MgO–C samples (1550‹ C, 6h). image).

The particular sensitivity of carbon with regard to oxygen is

the major defect of carbon­containing refractories. In order to
inhibit or slow down this oxidation, manufactures have added
a disperse system of metal additives such as Al,73) Si,73) Al–Si
eutectic alloy,74) Al/Mg alloy,75) Mg–B alloy76),77) or carbides
to the materials.
Jitsumori et al.78) studied the mechanism of adding the Al as
antioxidant in MgO–C refractories and its phase transforma­
tion during its service. The result has showed that an Al con­
tent of 5 mass÷ or more satisfactory prevented oxidation,
however, by coating Al on the MgO coarse grains, oxidation
was prevented using only 3 mass÷Al. It was found a fine Al
grain size are found to be more effective.
Fig. 7. Microstructure morphologies of Al2O3 formed in the matrix
3.3.1.5 Thermochemistry of MgO–C refractories contain­
of Al added of MgO–C sample after 1200‹ C. An Al4C3 core with a
ing various antioxidants
pore in its center covered by an Al2O3 shell (SEI).
Early thermodynamic analyses on the Al–C–O and Si–C–O
systems79) revealed that Al and SiC (or Si) suppress carbon
oxidation in two main ways. First by reducing CO to C, se­
condly by decreasing porosity (and so limiting permeation by Mechanisms for different antioxidants such as metallic
oxidizing gases) via volume expansions and C precipitation powders of Al, Si, Ca and Mg and their alloys behavior in
accompanying the reaction of Al or SiC (or Si) with CO. the MgO–C refractories have been investigated.73),74),88)
Later studies of the Al–C–O–N system80) has revealed that Al Through oxidation, a layer of alumina is formed according
either reacts with C to form Al4C3 or with N2 from the at­ to the reaction:–
mosphere to form AlN and further reduce CO to C that con­
Al(s){3/2O2(g) ¨ Al2O3(s) (See Fig. 6)
tributes to the carbon oxidation inhibition. The formation of
reaction products such as AlN, Al4C3 and Al2O3 improves At the melting temperature of the aluminum (660‹ C), the
mechanical strength.80) Yamguchi extended his study of fine layer of alumina at that time traps the liquid aluminum
the Al–C–O–N system and also examined Si–C–O–N and and breaks the film, consequently, releases molten aluminum
Zr–C–O–N systems81) discussing the influence of temperature (See Fig. 6). The released liquid aluminum reacts with the
and partial pressures of CO (or O2 ) and N2 on the stability of surrounding carbon to form aluminum carbide according to
metals, carbides and oxides. This work has showed that the the reaction:
antioxidants not only act as CO reducing agents, but also
4Al(l){3C(s) ¨ Al4C3(s) (See Fig. 6)
encourage the formation of an oxide dense layer at the hot
face, both mechanisms inhibiting carbon oxidation. B4C, as At a temperature of more than 1100‹ C, a further transforma­
an additive, reacts with CO to form B2O3 which reacts with tion occurs: the dissociation of the aluminum carbide accord­
MgO to form low melting 3MgOEB2O3(M3B).82) B2O3 and/or ing to the reaction:
M3B phases are liquids at high temperatures, their formation
Al4C3(s){3CO(g) ¨ 2Al2O3(s){9C(s)
blocks open pores and/or covers the carbon surface and thus
(See Fig. 7)
suppress its oxidation. For metal alloy additives, the reaction
mechanism may be considered as a combination of the The alumina combines with the surrounding magnesia to form
mechanism of each component. Depending on the reactivity MgO–Al2O3 spinel phase. The formation of these MgO–Al2O3
of each component with CO (or O2 ), they will function at a spinels phases occurs by a direct solid/solid reaction:
different stage.83) For example if an Al/Si alloy is added, the
MgO(s){Al2O3(s)) ¨ MgO–Al2O3(s) (See Fig. 8)
Al in the alloy acts first as the antioxidant. Once the Al is
exhausted, Si begins to work as the antioxidant. Later The spinel formation was confirmed by Karakus et al.,89) in
thermodynamics calculations on the behavior of metal the post­mortem MgO–C bricks.
antioxidants predict similar reaction mechanisms to those In the later case, the mechanisms involves reduction of the
suggested by Yamaguchi.84)–87) magnesia by the carbon according to the reaction:
 524 Carbon Based Refractories

Fig. 10. Saturation solubility of MgO in CMAS slag at 1700‹

C as a
function of slag Al2O3 content.

Fig. 8. BEI of the Al added sample after 3h at 1500‹

C, showing the
formation of Al4C3 and MA spinel.
3.3.1.6 Corrosion of MgO–C bricks
Zhang and Lee have reviewed the corrosion of MgO–C
refractories.91) Two main factors in the corrosion of MgO–C
refractories are the dissolution of MgO in the slag and the oxi­
dation of C by oxidizing the atmosphere or FexO and MnO
from the slag.92),93) Additing of Al metal powder to MgO–C
refractories has a positive effect on the corrosion resistance
but encouraging formation of a dense MgO layer and inhibit­
ing C oxidation, but it also has a negative effect by increasing
the saturation solubility of MgO in the slag (Fig. 10). As
shown in Fig. 10,94) in an acid slag, the saturation solubility of
MgO in the slag is high, so MgO dissolution in the slag is the
dominant factor affecting the corrosion resistance. In this
case, even if a dense MgO layer forms, it dissolves quickly
Fig. 9. BEI of the Si added sample after 3h at 1200‹ C. Many in the slag. Furthermore, Al2O3 formed from oxidation of
unreacted Si grains still remained in the sample, although SiC and Al will increase the saturation solubility of MgO in the slag
SiO2 began to appear. Mg2SiO4 was occasionally found in the sample.
(Fig. 10)94) counteracting the positive effect of Al addition,
so that it may not have an overall positive effect on the corro­
sion resistance. On the other hand, in a basic slag, because the
saturation solubility of MgO in the slag is low and is not sensi­
MgO(s){C(s) ¨ Mg(g){CO(g)
tive to the change of Al2O3 content in the slag(Fig. 10), the
In same way, Si metal is first transformed into silicon carbide, problem of carbon oxidation becomes more serious than the
then into silica and again into silicon carbide above 1500‹ C dissolution of MgO in the slag. Consequently, because Al ad­
according to the following steps: dition encourages MgO dense layer formation (which can
(1) Formation of silicon carbide remain at the refractories/slag interface for a long time) and
The silicon reacts with the surrounding carbon to form effectively inhibits C oxidation, it has a positive effect on cor­
silicon carbide according to the following reaction: rosion resistance. Ikesue et al.95) tested the effectiveness of Al
addition to MgO–C bricks in a basic slag (c/s3.0). They
Si(s){C(s) ¨ SiC(s)
found that Al addition improves the corrosion resistance. On
This reaction increases sharply at temperatures„1100‹ C on the other hand, Baker and Brezny96) found that Al addition to
the surface of silicon additives. MgO–C bricks resulted in severe corrosion in an acid slag (c/s
(2) The formation of vitreous silica 1.0). Asano97) used a rotary test to examine the effect of Al
Between 1100 and 1500‹ C a vitreous silica and carbon in two slags with basicity of 1.0 (slag A) and 2.0 (slag B). His
deposit according to the reaction: results(Fig. 11) showed that Al addition to MgO–C refracto­
ries improves their corrosion resistance slightly in the more
Si(s){CO(g) ¨ SiO(g){SiC(s)
basic, but not in the acid slag.
SiC(s){CO(g) ¨ SiO2(s){2C(s)
Hunold71) investigated the effect of Al, B4C, CaB6 and
Where SiO2 is stable in this temperature of less than 1500‹ C ZrB2 on magnesia carbon refractories. He found that the
(See Fig. 9) extent of corrosion decreasing from MgO–C without antiox­
At 1500‹ C, the formation of the forsterite is observed accord­ idants to MgO–C with antioxidant (Fig. 12). Adding boron
ing to the reaction: compounds creates a slight effect on the corrosion resistance
by a gas buffer. However, Al reacts with MgO to form spinel
2MgO{SiO2 ¨ 2MgO–SiO2
(MgO–Al2O3 ) and this dense spinel phase, in combination
Zhang et al.90) has confirmed the above mechanisms and with a gas buffer, improves corrosion resistance. However,
explained the reaction of the additive B4C with CO. He found the best results were achieved with a combination of Al and a
that B4C reacts with CO forming B2O3 which further reacts boron compound, which cause a progressive rise of the spinel
with MgO to form M3B according to the following equations: content. Experiments have shown that the Al/ZrB2 additives
provides the best corrosion resistance. Although Al/CaB6
B4C(s){6CO(g) ¨ B2O3(l){7C(s)
and Al/B4C are slightly less effective, they can also prevent
B2O3(l){3MgO(s) ¨ 3MgO–B2O3(s)
MgO–C bricks corrosion.
 Emad Mohamed M. EWAIS Journal of the Ceramic Society of Japan
Fig. 11. Corrosion of MgO–C bricks with and without Al addition
in acid slag A (C/S1.0) and more basic slag B (C/S2.0).
Fig. 12. Advanced corrosion of MgO–C samples as a function of the
added antioxidant.
Fig. 13. Relative corrosion rates of MgO–C refractories contain­
ing various antioxidant.
Recently,98) relative corrosion rates (corrosion index) of
MgO–C refractories with various additives have been investi­
gated. The results (Fig. 13) compared to the additive­free
refractory, the corrosion rate increased by `26÷ with addi­
tion of Al{Si, by 35÷ with addition of Si and by `97÷
with addition of B4C. Corrosion only decreased slightly (by
`3÷) by addition of Al, but decreased markedly (by`30÷)
by additives of Al{B4C. This is rationalized by the inhibition
of carbon oxidation due to the addition of both Al and B4C
via the following: Firstly, CO(g) is reduced back to C by Al
and/or B4C via e.g. Reactions (1), (2), (3). Secondly, FexO
and MnO from the slag reduce via e.g. Reactions (4), (5).
Thirdly M3B liquid formed with refractory via e.g. Reaction
(6), fills the pores between C (mainly graphite) covering
the C surface (Figs. 14 and 15). These layer MA crystals are
often coexisted with M3B phases, suggesting that at the test
temperature M3B liquid might have played a role in their
112 [10] 2004 525
Fig. 14. Corroded microstructure (BEI) of Al{B4C added refrac­
tory. The dense MgO layer was severely penetrated and corroded by
the slag, but a thin decarburized layer and a slag penetrated layer were
observed. MMgO, Vvoids, Ggraphite, Sslag. A: uncorroded
layer; B: slag penetrated layer; C: decarburized layer; D: dense layer;
E: slag layer.
Fig. 15. High magnification BEI of uncorroded layer shown in
Fig. 14, showing that large MgAl2O4 (MA) crystals coexist with
MgO¥3B2O3 (MB) formed between graphite (G) in the matrix.
formation and growth. As reported by Surquru,99) boron­con­
taining liquid has a strong mineralizing effect on MA
crystallization. This fact further indicates that graphite in the
matrix which was protected from oxidation was also bonded
together by MA crystals at the test temperature. Now the
negative effect of these additives on the MgO dissolution is
similar to the Al or B4C single additions. Additions of Al{
B4C would accelerate MgO dissolution by increasing the local
slag Al2O3 and/or B2O3 contents.
2Al(g, l){3CO(g){MgO(s)MgAl2O4(s){3C(s)
(1)
2Al4C3(s){2MgO(s){6CO(g)2MgAl2O4(s)
{9C(s) (2)
B4C(s){6CO(g)2B2O3(g, l){7C(s) (3)
2Al(g, l){3FexO(l)3xFe(g, l){Al2O3(s) (4)
2Al(g, l){3MnO(l)3Mn(g, l){Al2O3(s) (5)
On the other hand, the carbon content plays an important
role in the depth of slag penetration. Hayashi62) reported
that the addition of carbon reduces the penetration of slag
(Fig. 4).
Great improvements with respect to corrosion resistance of
magnesia carbon refractories were done based on fused MgO
grains. This conclusion was understood from the effect of
large crystal size of the fused magnesia comparing by dead
 526 Carbon Based Refractories
Fig. 16. SEM­image illustrating a small steel droplet at the surface
of the refractory substrate in the experiment in which the interaction
between the austenitic stainless steel (0.047÷C) and MgO–C.
Fig. 17. SEM­images illustrating the interface between ladle slag and
unused MgO–C refractory.
burned one.100),101)
3.3.1.7 Wear of MgO–C refractories
Early wear mechanisms for MgO–C refractory bricks with
different content of residual carbon (8–20÷) have been ex­
tensively described after service in EAFs and BOFs. The
writers60) concluded that the wear is occurred by hot face cor­
rosion­erosion of a thin decarbonized hot face zone. Further­
more, they agreed with conclusion of carniglia102) based on
thermodynamic analyses of carbon bonded magnesia brick in
BOFs, whereas decarbonization is principally occurred by the
action of oxidation from either the furnace atmosphere direct­
ly or through the generally­prevalent slag coating(CO2, O2,
Fe2O3 ). This further conclusion concur with the results that
concluded from sporadic evidences of Mg gas oxidation–depo­
sition textures found in some post mortem samples, that the
MgO–C reaction must be considered aeminorfbut significant
contributor to brick wear.
The high wear durability of MgO–C refractories is based
on the high chemical stability of MgO and also slag's
limited capability to infilterate into the carbon­containing
materials.103),104) Mukai et al.105) proposed the wear mechan­
ism of refractories contains oxide and graphite due to the
contact with steel and slag as following. (1) Refractory
material is initially covered with slag film which wets oxide
material and dissolves it in favour of graphite. This provides
a graphite rich layer at the surface. (2) Molten metals wets
and dissolves graphite in favour of oxides which results in the
disappearance of the graphite layer and the surface is again
covered with slag and the process is repeated. In other words,
the oxide material is attacked by the slag whereas the graphite
is attacked by the steel melt. Heikkinen et al.106) investigated
the chemical wear mechanism of MgO–C refractories by meas­
uring the wetting angles between steels and slag and MgO–C
refractories. The results support a wear mechanism in which
the graphite is either dissolved in steel (Fig. 16) or reacts with
chemically unstable oxides in the slag (e.g. FeO) (Figs. 17 and
18) and the binder material of the refractories leading to the
Fig. 18. SEM­images illustrating the interface between ladle slag and
MgO–C refractory wetted austenitic stainless steel (0.047÷C) (left
image) and a metallic droplet at the interface between ladle slag and
MgO–C refractory (right image).
Fig. 19. SEM­image illustrating small MgO­particles inside the slag
phase near the slag­refractory­interface.
detachment of the MgO particles (Fig. 19). The results also
indicate that the wear of the MgO–C material caused by the
subsequential contact of slag and steel is greater than the wear
that was caused by the slag and steel separate.
3.3.2 Carbon containing dolomite refractories
Metallurgical and economical advantages have favoured the
utilization of dolomite refractories in the steel production and
hence steel producing furnaces are the majors consuming cen­
ters of dolomite refractories. In steel industry, application of
unfired dolomite refractories is mainly confined to the lining
of BOF converters, BOF ladies ladle furnaces, VD/VAD/
VOD/AOD vessels and electric arc furnaces.47),62),107)–113) An
improvement has been made in such bricks in which car­
bonaceous material such as pitch, tar and/or flake or vein
graphite were used to form the bond of dolomite­carbon
bricks.21),114)–119)
The addition of carbon to dolomite bricks enhances the
thermal shock resistance where both thermal conductivity and
the coefficient of dilation decrease (See Fig. 20).120)
Corrosion of refractory products can be controlled by
decreasing or preventing the slag or metal infiltration. This
can be achieved via controlling the pore radius of refractory
(r ), the slag's wetting angle of contact the refractory brick
(f), the time (t ) and viscosity of the slag or metal (h) accord­
ing to the following expression:–
I s (cos f)rt/2h
It was reported that the addition of carbon lowers the
porosity of the refractory products and increases the wetting
angle (See Fig. 21). Further carbon enrichment also reduces
the iron oxide in the slag, raising the eutectic melting point of
the slag in the system CaO–SiO2–FeOx from approximately
1300‹ C to over 1600‹ C.
Carbon addition plays an important role in load bearing
capacity of dolomite bricks. Recently,121) a study has been
 Emad Mohamed M. EWAIS
Fig. 20. Coefficient of linear dilation of bricks with different carbon
contents.
Fig. 21. Wetting behavior of slag on MgO–C refractory.
Fig. 22. Deformation of BOF slagged tempered different tar/pitch­
bonded dolomite bricks as a function of temperature under load (a:
3.5 kg/cm2 and b: 4 kg/cm2 ).
carried out on the attack under load of tempered tar/pitch­
bonded Egyptian dolomite by BOF slag. It was found the in­
crease of residual carbon improves the refractoriness under
load (See Fig. 22). Such improvement was described depend­
ing on the inhibition behavior of carbon due to its non­wet­
tability by slag.
3.4 Carbon containing non­basic refractories
3.4.1 Clay­bonded graphite refractories
Crucibles are refractory, coarse ceramic vessels with good
thermal conductivity and low electrical resistance. Two types
of crucibles in regards to their type of bond (clay and carbon
bonded) and forming or shaping process such as plastic or
isostatic pressing were reported.122) A Clay bonded (plumba­
go) crucible is composed primarily of mineral flake graphite
mixed with granular refractory materials and bonded with
clay. This type of crucibles has been familiar for many years
for stoppers and nozzles for bottom­pour steel ladle, and the
melting of metals (ferrous or nonferrous metals) for foundry
purposes.123) In present day practice, granular refractory
materials e.g. SiC to some extent, sillimanite, fused alumina
and calcined firclay are used. In recent years a protective glaze
layer is applied during the manufacturing of these types of
crucibles to prevent the oxidation of carbon.
Carbon­bonded graphite with remarkable enhancement in
resistance to thermal shock and the strength was developed by
Journal of the Ceramic Society of Japan 112 [10] 2004 527
Fig. 23. Magnesia carbon and flow control refractories.
addition of SiC (purity degree, 94–96÷) and Si metals(purity
degree, 95–98÷). This enhancement was attributed to high
thermal conductivity and low thermal expansion of SiC that
added. Further development was reported based on forming
technique, in particular, isostatic press.124) Isostatic pressed
carbon­bonded crucibles with resin bonded and clay bonded
one has proved positively great influence on the property value
in particular bulk density and the thermal conductivity of
crucibles compared by the plastic pressing.124)
The life of the refractory lining of a blast furnace is one of
the principal factors determining the length of a campaign.
One approach to the extension of the life is to minimize the ex­
tent of chemical attack through the use of cooling. To kept the
interface temperature between the refractory and the furnace
burden below that at which reaction can occur, clay­bonded
natural flake graphite (plumbago) was recommended as heat
transfer medium in the blast furnace.125),126)
3.4.2 Tapholes refractory mixes
Different types of tapholes mixes were reported: clay­bond­
ed (fireclay, grog, coke), tar bonded (fireclay, grog, coke)
and upgraded tar bonded (fireclay, grog, coke, SiC) tapholes
mixes.127) Because of the insufficient quick setting property of
coal tar, a thermosetting synthetic resin such as phenolic resins
were developed for bonding tapholes mixes (fused alumina,
SiC, fireclay coke, Si).128)
3.4.3 Non­clay­bonded graphite refractories
A large number of different non basic clay refractories
containing carbon were reported including: Al2O3–C,129),130)
ZrO2–C, ZrO2–CaO–C,131) Al2O3–SiC–C,132) Al2O3–ZrO2–
C,133) Al2O3–SiC–C–SiO2–ZrO2 and Al2O3–SiO2–C and Al2O3­
spinel­C134) and SiC–C.135)
Most of these products are manufactured by pressing the
oxide isostatically with resin or pitch and flaky graphite in the
form of shrouds, monobloc stoppers and submerged nozzles
(See Fig. 23). Coking of these materials up to 1000‹ C forms a
carbon bond which possesses some superb properties e.g. flex­
ibility of the bond and enhancement of the thermal shock
resistance.136) The addition of silicon metal as antioxidant is
recommended to improve the strength of the material during
service.
Takeshita et al.137) has investigated the effect of the SiC
addition on the properties of Zirconia graphite. They found
that SiC addition prevent the embitterment of the matrix and
enhance the thermal conductivity and decrease the thermal ex­
pansion coefficient.
The corrosion rate of Al2O3–C in melts containing titania
has been studied.138) The authors found that the corrosion rate
is decreased with addition of graphite and Zirconia in refrac­
tories. The corrosion behavior is due to the oxidation of
graphite by the oxide melt and the formation of deteriorate
layer composed of FeOESiO2, SiZrO4, FeOE3CaO, 2CaOE
SiO2 and CaOESiO2.
 528 Carbon Based Refractories
Fig. 24. Evolution of BOF linings: pre­1970, tempered pitch­bonded doloma: (b) early 1970s, magnesia­enriched tempered pitch­bonded dolo­
mite: (c) late 1970s, pitch­tempered fired magnesia, and: (d) 1980s (numbers indicate the amount of carbon, in percent, in the carbon­bonded
magnesia graphite brick.
3.5 Application of refractory containing carbon
In the late of 1970s, fired, pitch­impregnated magnesia lin­
ings were introduced because of the reduced hydration of
magnesia and beneficial effects of carbon with respect to
wetting by slag and thermal shock (Fig. 24). These modifica­
tions increased lining lives to 800–900 heats. However, ad­
vances in BOF steelmaking technology, such as the introduc­
tion of the top and the bottom blowing as well as combined­
stirring and foamy slag procedures, meant that improved
refractories were needed. The development of carbon­bonded,
graphite­reinforced magnesia brick fulfilled this need, provid­
ing a refractory with excellent slag resistance because of the
nonwetting carbon/graphite and improved thermal shock
resistance because of its high thermal conductivity and crack
propagation­resistant microstructure.139)
The water cooling as technical renewal in the upper part of
the EAF furnace (wall) and also partly in the roof represents
and the innovation which helped Steelmakers to increase its
productivity and decrease the reduction cost included oxygen
lancing, oxyfuel burners, slag foaming techniques, EAF bot­
tom stirring, scrap preheating, slag free tapping and hot heel
practice, DC operation and process automation. These inno­
vations have direct impact on the performance of the lining
and needs much attention during the refractory production.
Magnesia containing carbon brick was recommended to meet
these requirements which overcame these troubles.140)–142)
Molten steel is transferred from the primary furnace (BOF,
AOD, EAF) to the continuous casting using steel ladles,
which are large vessels lined with ceramic refractory materials.
The most common refractories that are used in integrated steel
plants are high Al2O3­and especially MgO–Al2O3­based
materials.103),143)–149) It is common that the wear of the
refractory materials is the fastest in the slag line where the
refractories are in contact with both steel and slag.103),149)–151)
Therefore more resistant materials consisting mainly of
MgO and carbon were recommended for using in steel ladle
slaglines.103),147)–150) Use of carbon­bonded magnesia enhanced
the performance of BOF from 415 heats to 1350 heats.152)
In the secondary steelmaking process, there are many oper­
ating processes and conditions such as vacuum refining and
ladle refining, etc. refractories are therefore used in unique
combinations of various bricks to meet such diversified condi­
tions. In any operations, however, the refractories are used
under the following severe conditions: (1) High temperature
of the steel and long holding time; (2) Wide variation of slag
composition and fluidity of molten steel; (3) Large abrasion
by stirring of molten steel; (4) Many cases of vacuum treat­
ment; and (5) Large thermal changes. Steelmakers, however,
are introducing secondary steelmaking process rapidly in ord­
er to cope with requirements in wide scope such as steel quality
improvement, higher productivity, and saving of resources
and labor. The refractories used for steel ladle refractory bar­
rels and bottoms have been lined with high alumina or dolo­
mitic refractory products. Dolomitic products have weighed
heavily toward minmill shops and high alumina toward in­
tegrated mills. On the other hand, carbon based magnesia and
dolomite magnesia, alumina, magnesia spinel, magnesia­alu­
mina and dolomite refractories have been introduced as new
types for ladle.153)–161) However, the introduction of pitch­
bonded MgO–C bricks into slag zone of the ladle and resin
bonded alumina magnesia graphite bricks for ladle furnace
barrel and bottom applications gave high performance as a
result of the formation of the spinel dense layer in the refrac­
tory/slag interface.158),162),163)
It is common practice in the continuous casting of steel to
utilize special refractory materials and shapes to control the
flow of the molten steel and to protect the liquid metal against
oxidation as it is teemed from a ladle to a tundish and thence
to the mold or molds. Among such special refractory shapes
are slide gate plates and/or stopper rods which are used to
control the flow of the molten metal. In addition, specially
shaped refractory pouring tubes are associated with the ladle
 Emad Mohamed M. EWAIS Journal of the Ceramic Society of Japan
and the tundish, such as submerged ladle shrouds and nozzles
which are employed to protect the molten metal from ambient
oxidation during the teeming/casting operations. These
refractory shapes are subjected to severe operation conditions
and must be able to withstand thermal shock, as well as the
chemical/erosive attack of molten steel and slag. For that
steelmaking operation, alumina, zirconia, clays, magnesia and
silicon carbide refractories containing carbon are commonly
used.164),165)
In modern steel mills, steel is teemed from ladles and tun­
dishes through sliding gate valves at the bottom of these ves­
sels. The sliding gate valves comprise two or three plates hav­
ing holes therein that can be brought into and out of registry
by relative movement of the plates. The plates of the sliding
gate valves must have good erosion resistance as well as excel­
lent mechanical properties at elevated temperatures. The
plates and associated nozzles are made of various refractory
compositions. Recent development of aggressive grades of
steel has necessitated the creation of different types of ceramic
composition, which is capable of controlling the flow of the
molten steel under severe casting conditions. Impregnating
fired carbon bonded magnesia refractory (including a mag­
nesia­alumina spinel and aluminum carbides which precipitate
to the bonding phase forming in situ during the high tempera­
ture firing treatment) was recommended for slide gate plates,
inserts for such plates and for pouring nozzles.166),167)
Shroud and submerged nozzles are used for protecting from
reoxidation of steel ranging with ladle­tundish and tundish
mold, respectively. Alumina graphite and Al2O3–SiC–C have
been developed for phase purposes.152)
4. Concluding remarks
Upon reviewing the carbon based refractories, it can be
concluded that:
(1) Carbon based refractories includes carbon bricks/
blocks as soley carbon refractory materials, carbon containing
basic refractories (magnesia and/or dolomite) and carbon
containing non­basic refractories (oxide and clay).
(2) There are various techniques applied in the manufac­
turing process that depends on the product types.
(3) There is a discussion continuing about bonding
materials (resin and pitch) from environmental point of view
due to its effect on the quality of the ultimate carbon based
refractories.
(4) Because the oxidation of the carbon is the commonest
problem, the addition of antioxidants is very important.
However, the complete understanding of the behavior in terms
of corrosion and wear mechanism and thermochemistry of the
antioxidant is very important for evaluating the service life.
(5) Thermal and mechanical properties of these types of
refractory materials is remarkable.
(6) These materials have wide range of applications in the
iron and steel industry. Their applications are contributed in
the reduction of the refractory consumption and considered as
one of the refractory classes that meet with the development of
steelmaking process.
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