CERAMICS
of their “acidity” and “basicity”.
GENERAL
Ceramics are one of the oldest products
used by mankind. They are still used in large
quantity for pottery, porcelain, sanitary
equipment, bricks, etc . . .
At the very beginning, they were
manufactured from raw materials based on
different silicate components. (clay)
To satisf y the ever more demanding
applications, the pure oxides like
MgO Al203 Zr02 Cr203
together with carbide, boride, nitride are now
used and belong to the range of ceramics
which can now be divided into two main
families
Classical Ceramics Technical Ceramics
DEFINITION
As a very general assumption, we can
consider Ceramic materials those industrial
products based on inorganic materials which
used as powder are then formed with
different systems and fired at a temperature
normally lower than the melting point. (Fig.
3.1)
THE RAW MATERIALS
Ceramic products (with the exception of
Carbon and Graphite products) are normally
composite, that is to say they have atoms
with minimum of two elements i.e.
- MgO, Al203, Si02, SiC, Ca0, Si3N.
The oxides which are the main components
Fig. 3.1
of ceramics can be classified as a function
- Basic oxide Mg0, Ca0, Li02 ,
Na20, K20
- Acid oxide Si02 , B203 , Zr02
- Amphoteric Al203 , Cr203
As general information, the acid oxide easily
reacts with basic oxide at a temperature
depending on the nature of components. As
result of these reactions we can have:
- very well defined components
- formation of a solid solution
What can happen depends on the original
components and is defined and can be
predicted through the use of the phase-
diagram where the possible combinations of
two or more components are shown in
relationship with temperature. (Fig. 3.2, 3.3,
3.4)
Ceramic Engineers, utilize the possibility of
reaction between different materials to
design ceramics having well determined
characteristics, starting from powders [raw
materials].
THE CERAMIC BONDING
The process to manufacture ceramics has
been used in the world for centuries. The first
raw material used was clay which was easy
to use since with the addition of water
becomes plastic and very easy to form to any
shape.
Once dried the clay becomes hard and after
firing to a temperature higher than 1000°C it
becomes strong and brittle.
Chp. 3 5
 Fig. 3.2

Fig. 3.3

Fig. 3.4

Chp. 3 6
 Fig. 3.5
Nowadays the process of manufacturing
modern ceramics is practically the same. The
tendency is to eliminate the clay achieving
the bond through the right additions and
helping the forming through organic
plasticiser. (see Fig. 3.5)
What happens during the firing cycle both
for clay based ceramics or modern ceramics
is practically the same.
The additions, following the law graphically
represented through the phase diagrams,
will create a liquid eutectic which will
penetrate into the interface of the grains of
the ceramic material during the firing cycle.
The eutectic is a mixture of two or more
components having a very well defined
concentration and a melting point lower than
the individual components. The formation of
the eutectic occurs at a very well determined
temperature (temperature of eutectic) which
depends on:
- nature of components
- concentration of components
When it cools down the liquid eutectic
becomes vitreous and then solidifies,
building up the bond of the ceramic
materials. When the temperature during
application of the ceramic is higher than the
eutectic temperature the properties of the
ceramic are reduced. It is not always possible
to have a eutectic formed at a higher
temperature than the application
temperature. When that is achievable, there
is the possible formation of a glass which has
a high Youngs modulus which will decrease
the resistance to thermal shock.
DIRECT BONDING (SINTERING)
Since impurities in the raw material result in
low melting point eutectics with consequent
reduction in properties; the use of high purity
components is necessary for high
performance ceramics. In this case the bond
is achieved in the solid phase at very high
temperature. The bonding occurs between
the grains of the matrix where atoms
combine together one or more pairs of
electrons (direct bonding). Ceramics having
that bonding system will have a high fusion
point, good electrical insulation properties
and a high Youngs modulus.
CHEMICAL BOND
This bonding system is based on chemical
reaction between the matrix grain, which can
be achieved at low temperature (@800°C)
when acids are added in low concentration
to the matrix. The bond achieved exhibits
excellent mechanical properties and erosion
resistance (it is prone to thermal shock
without silica addition).
During use the chemically bonded product
will develop a ceramic bond but this change
does not affect the behaviour of the product
in use. The most commonly known chemical
bond is based on Alumina phosphate
formation.
HYDRAULIC BOND
Like the chemical bond the hydraulic bond,
based on the use of cement, requires low
temperature to be achieved. The cement
usually based on calcium aluminate, reacts
with water and binds the grains of the matrix.
Chp. 3 7
The use of this type of bonding is specially
adopted to form difficult shapes through
casting, vibro casting or even gunning.
The disadvantage using lime, (component of
cement) which creates low melting phases
at high temperature, is nowadays practically
solved using ultra low cement formulations.
PROPERTIES OF THE CERAMICS
The main properties considered in the design
and manufacture of ceramics are:
- apparent porosity (AP)
- open and closed porosity
- permeability
- pore size distribution
- cold and hot modulus of rupture (MOR)
- modulus of elasticity (E)
- expansion coefficient
When we speak about ceramics we always
have in mind materials which are ‘hard and
fragile’.
That definition is very true if we look at the
diagram showing deformation versus load
(Fig 3.6).
This shows that it is possible for ceramic
materials to reach breaking point when a very
small load is applied. Ceramic materials and
refractories in general have excellent
properties in compression but very poor
behaviour in flexion and shear.
When we have to consider what is the best
performing ceramic for a particular
application the first thing we consider is the
chemical composition to understand the
­ Pure Iron
½ to thermal shock.
Load
Metals and Alloys
Ceramic Materials
Deformation
½
­
Fig. 3.6
Chp. 3 8
reactivity of the material in the working
environment and then the properties like
those already listed AP, MOR, E etc. All these
physical properties are used by ceramics
engineers to design ceramics and these
properties are monitored during the
manufacturing process (SPC).
There is one very important property when
we consider materials for use in continuous
casting where there is rapid large change of
temperature.
This property is thermal shock resistance
which defines the properties of a material to
resist rapid, large changes in temperature
and is defined by the following formula:
- thermal shock resistance
st
R = f(n)
Ea
st : tensile strength
E : modulus of elasticity
a : thermal expansion coefficient
f(n) : function of Poisson coefficient
depending from test piece shape
The value R is expressed in °C and
represents the maximum variation of
temperature (DT) which a test piece can
bear without breakage (see table 3.1, 3.2).
Other properties which determine the final
use of the ceramics are:
- resistance to corrosion from external
action (steel slag) which depends on:
- composition
- wettability of material
- surface contact angle
Ceramics having a ceramic bonding exhibit
a high value of E and therefore are sensitive
CARBON BONDED REFRACTORIES
The growth and development of the
continuous casting technique brought to the
market a high demand for special refractories
capable of satisfying the demand of always
higher performances.
The definition of the main properties of these
refractories can be summarized as follows:
- High thermal shock resistance
- Resistance to erosion of a large range
of steel grades
- Resistance to the slag and flux attack
- Stable bonding system in the range of
temperature of use
Fused silica, the first material used for a
 silica no phase
hase
silica p

te
esi
agn
om
om
ica i t e

chr
sil n e s
te
no m a g
ate
s ilic

mi
ino

alu
m
alu
nite
ma
sili
silica glass

Fig. 3.7 - Thermal Conductivity of Refractory Brick Fig. 3.9

Fig. 3.8 - Specific Heats of Refractory Brick

Chp. 3 9
 Thermal Shock Resistance Parameters

Parameter Physical interpretation/heat

designation Parameter type Parametera transfer conditions Typical units

R Resistance to fracture initialtion u(1 - u) Maximum DT allowable for steady heat °C

aE flow

u(1 - u)k
R1 Resistance to fracture initiation Maximum heat flux for steady flow cal/cm• sec
aE

u(1 - u)aTH Maximum allowable rate of surface

Rn Resistance to fracture initiation aE heating cm2• °C/sec

E Minimum in elastic energy at fracture

Rm Resistance to propagation damage u2(1 - u) (psi)-1
available for crack propagation
7E
Rm Resistance to propagation damage u2 (1 - u) Minimum in extent of crack propagation cm
on initiation of thermal stress fracture
1/2
Rst Resistance to further crack propagation u7 ) °C/m1/2
( a2E Minimum DT allowed for propagating
long cracks

Table 3.1 Thermal shock resistance parameters.

Material Thermal Thermal Elastic Strength R

Cond. Expans. Modulus

MAGNESIA 7.1 13.5 30 15 25

ZIRCONIA 2.3 10.2 22 20 65

ALUMINA 6.3 8.8 53 40 65
MULLITE 3.8 5.3 10 10 130

ALUMINA GRAPHITE (c22%) 15 4.0 1.5 1.2 140

GRAPHITE 63 2.2 1.3 2 550
SILICA 2.5 0.5 10 4 600

R is a relative measure of resistance to thermal shock.

Table 3.2 Thermal shock resistance of various materials

Oxidizing Coefficient of Thermal Conductivity

Melting Atmos- Hardness Linear Expansion cal/(see cm2) (°C/cm)
Point pheres, Mohs’ Temperature Temperature Porosity,
Material Formula °C °C Scale °C E x 107 °C % C x 10?

Alumina Al2O3 2015 1950 9 20-1580 80 1200 23 57

Beryllia BeO 2550 2400 9 20-1400 95 1200 5-10 393
Calcia CaO 2600 2400 4.5 20-1200 136 1000 9 170
Magnesia MgO 2800 2400 6 20-1400 140 1200 22 61
Silica SiO2 1728 1680 7 20-300 430a 1100 ... 38
(crystalline) 00-1100 30

Silica (vitreous) SiO2 ... ... ... 20-1250 5 ... 0-9 33

Thoria ThO2 3300 2700 7 20-1400 95 1200 17 0
Zirconia (stabilized) ZrO2 2600 2500 7-8 20-1200 55b 1200 28 22
Mullite 3Al2O3 • 2SiO2 1830c 1800 6-7 20-1320 45 1200 30 64
Spinel MgO • Al2O3 2110 1900 8 20-1250 90 1300 36 50
Zircon ZrO2 • SiO2 2420 1870 7.5 20-1200 55 1000 30 50

a Depends upon crustalline forms. b Depends upon degree of stabilization. c Incongruent.

Table 3.3 Properties of various materials.

Chp. 3 10
 Stabilised
Thermal Expansion

non-stabilised

Temperature (°C)

MONOCLINIC a = 5.165 A
b = 5.191 A
c = 5.304 A
a = b = 90°
g = 98.9°
Density: 5.830 g/cm3

TETRAGONAL a = b = 5.094 A
c = 5.177 A
a = b = 90°
Density calculated: 6.10 g/cm3

CUBIC a = b = c = 5.124 A
a = b = 90°
a = b = g = 90°
Density calculated: 6.09 g/cm3
Fig. 3.10 Fig. 3.11

Fig. 3.12 Fig. 3.13

Chp. 3 11
submerged nozzle, does not combine all
these properties.
The use of composite ceramically bonded
refractories did not ensure the achievement
of these properties.
The solution of the problem arrived with the
use of graphitized carbon bonded material
manufactured through an isostatic pressing
process.
These types of refractories have as main
components Alumina, Zirconia, Graphite.
Each component acts in synergy to protect
the other from the various attacking
mechanisms.
The role of each component can be
summarized as follows:
Alumina : provides resistance to the
erosion of molten steel
Zirconia : provides resistance to the
erosion of mould flux
Graphite : provides resistance to thermal
shock and prevents penetration
by mould flux or slag.
THE GRAPHITE
The graphite is an allotropic form of carbon
(Fig. 3.14) as well as diamonds. The shape
of the carbon crystal is hexagonal and
graphite can be found in nature in the form
of flakes.
But what is important is that graphite exhibits
properties which make this material
exceptional.
6.70 6.16
< 100 Å > 1000 Å
al bl cl
Fig. 3.14
Graphite, Diamond and Polymeric Carbon Structures
Chp. 3 12
It is not wettable by most liquids
included molten steel.
This property improves the corrosion
resistance of the material to which graphite
is added because there is less infiltration of
steel inside the graphite based refractories.
It has a low thermal expansion
coefficient.
Added to refractory the graphite decreases
the thermal expansion of the mix and
automatically increases the thermal shock
resistance.
It has a good thermal and electrical
conductivity.
This means that graphite increases the
thermal conductivity of the refractory to which
it is added whilst decreasing the temperature
gradient. In another way, we can say that
graphite increases the resistance to thermal
shock.
It has high elasticity/plasticity of the
flakes.
This means that graphite improves plasticity
of the material to which it is added. This
characteristic is useful during the
manufacturing process of the graphite based
material.
Graphite does not develop a ceramic bond
with ceramic oxides and this is probably the
main reason for its success in imparting
thermal shock resistance. It provides
discontinuities in what would otherwise be a
tightly bonded ceramic network. These
discontinuities can be thought of in much the
same way as pores, acting as a “sink” for
thermal stress, thereby preventing crack
propagation. Unlike pores, however, graphite
does not allow ingress of attacking fluxes by
virtue of its property of non wettability.
In terms of measurable parameters which
may influence thermal shock resistance, the
effect of adding graphite to refractory oxides
is, in all respect, favourable.
As we can see in Fig. 3.15 graphite reduces
thermal expansion and the modulus of
elasticity while increasing strain to failure and
thermal conductivity.
THE CARBON BOND SYSTEM
The texture between the oxides assured by
 carbon).
EFFECT OF GRAPHITE ON PHYSICAL PROPERTIES
OF REFRACTORIES It is inside this structure where the ceramic
oxides are trapped and “bonded” together.
The advantages of the carbon Bond System
are:
- A lower firing temperature is needed to
Strength develop the bond
Expansion - Strength retention at high temperature
Modulus
- Better thermal shock resistance that
results from the “non-rigid” nature of the
Conductivity bond.
- Resistance to flux attack.
All these properties are directly connected
to the peculiar characteristics of carbon.
Fig. 3.15
ISOSTATIC PRESSING
the ceramic bond creates problems when the All the processes used to shape a refractory
temperature of eutectic is reached material introduce stresses in the final
(collapsing of properties). product.
Refractories having a direct bonding system Some processes offer limitations in length
or a temperature of eutectic higher than that and dimensions, others do not offer the
of molten steel, offer very poor properties in required properties of the final product.
term of thermal shock.
For the Al 2O 3-G material, Vesuvius first
The problem created by these introduced the isostatic pressing process to
characteristics, which do not meet the shape the product for three main reasons:
requirements for the refractories to be used
in continuous casting applications, is solved - to introduce into the product the
through the use of the “Carbon bond minimum stress possible.
system”. - to have the possibility to manufacture
the long patterns required in the
This type of bonding is achieved after firing continuous casting application.
ceramic material to which is added a - to manufacture multimix composite
phenolic resin. patterns using only one pressing cycle.
The structural model of this bonding system THE PROCESS
is shown in Fig. 3.16. The flow chart illustrating the main steps of
It consists of a dense glassy phase of the process is shown in Fig. 3.17.
interconnected ribbon-like carbon (curly
MIX PREPARATION
The preparation of the mix is one of the most
important parts of the process because the
mix properties largely determine the
Typical strong confluence characteristics of the final product.
The formulation and the preparation of the
mix is an important know-how of the process
Weak confluence and for that reason only limited information
is given here.
Vesuvius issues all the specifications for the
Lc Lc Lc raw materials used for the mix preparation
and operates an entry control when
specification of the mix material is verified.
Lc
Once batch weighed the raw materials are
delivered to the mixer where binder is added.
After mixing the mix is tested to make ensure
the correct compaction will be obtained at
the pressing stage. Batches of one ton are
Fig. 3.16 prepared and delivered to all the
Chp. 3 13
 VISO PROCESS
Raw Materials Binding Material

¯
Mixing/Blending

¯
Pressing

¯
Curing
RR/LS SEN/SES/TN
¯

Glazing Firing

¯ ¯
Firing Machining

¯ ¯
Finishing Glazing

¯ ¯
Product Finishing

Fig. 3.17 Product

manufacturing plants. In order to guarantee CURING, GLAZING, FIRING (FIG. 3.19, 3.20)
the consistency of mix, Vesuvius supplies Once pressed and demoulded the pieces
mixes only from selected plants. are fully cured (dried) and then follow different
routes in the process depending on the
PRESSING (FIG. 3.18) product type:
Pressing of the pieces
- stoppers and ladle shrouds will be glazed,
- Several batches of mix are blended dried and then placed in a kiln for open firing
together to optimize the mix (oxidizing atmosphere).
characteristics
- subentry nozzles and shrouds are placed
- Hoppers are then loaded with different
in a kiln and closed fired (reducing
mixes
atmosphere) and after firing are ground to
- Mix from the hoppers is used at the filling
final dimension and then dipped in baths of
station to fill the moulds
glaze, dried and finally sent for packing.
These moulds have two main components:
- an external flexible bag in plastic FINISHING AND PACKING
- an internal mandrel in metal
It is important to remember that any part of
the manufacturing process is subjected to
After filling the mould is sealed and placed
the procedure of QA and that all the pieces
in a pressure vessel where the process of
are identified through all the process
isostatic pressing is carried out. The vessel
(traceability). Statistical Process Control is
is filled with water and pressurized and the
also applied to guarantee the complete
pressure is therefore equal on all the surface
follow up of the manufacturing process, the
of the bag (Pascals law). This is isostatic
detection of trends and the feedback of
pressing where products are pressed free
corrective actions.
from stresses.

Chp. 3 14
Fig. 3.18

Fig. 3.19

Chp. 3 15
 Fig. 3.20

THE MATERIALS
The family of Isostatically pressed carbon
bonded material comprises a large number
of mixes developed for different and
particular applications. The final formulation
of a mix has to have thermal and chemical
properties which are suitable for the
application.
The main body of the mix is called the matrix
and uses Al2O3;MgO and ZrO2 as the main
components. Other important components
are the graphite and the carbon of the
bonding and finally special additives which
impart special characteristics to the mix and
protect the carbon and graphite from
oxidation.
Fig. 3.21 shows the main components of the
Viso mix, which are usually isopressed, and
how they combine to give the final properties
of the product.

OXYDE-GRAPHITE THERMAL

Al2O3
Metals MATRIX 50-90% MgO
Carbides
Nitrides ADDITIVES 0-10%
Borides
Low GLAZE
melting

GRAPHITE 4-40%
CARBON BOND
MECHANICAL CHEMICAL

Fig. 3.21

Chp. 3 16
Fig. 3.22 shows the main components of a
Viso mix by weight and volume.
Table 3.4 shows the role of the components
of a typical Viso product.
EROSION RESISTANCE
Viso material has to be resistant to erosion
from both steel and slag. It also has to be
protected from oxidation by the atmosphere
during both the preheat and casting cycles
(oxidation)
EROSION BY STEEL
The rate of erosion by the steel depends on
the type of steel being cast and Fig. 3.23
shows the effect of steel grade on the erosion
rate.
Steels which have a high oxygen content
produce the most erosion and Fig. 3.24
shows the relation between free oxygen in
the steel and erosion rate.
The manganese content of the steel also
affects the rate of erosion and Fig. 3.25
shows the relation between manganese
content and erosion rate of pouring tubes.
EROSION BY SLAG
During continuous casting slag forming
powders are added to the exposed surface
of the steel in the mould for the following
reasons:
- to insulate the steel and prevent
solidification of the exposed surface

TYPICAL VISO MIXES

BY WEIGHT BY VOLUME

30%
30%
Carbon 50%
Refractory Grain
(Graphite 50% Carbon
& Bonding Refractory Grain
(Al2O3, MgO,
Carbon) (Graphite
ZrO2)
(Al2O3, MgO, & Bonding
ZrO2) Carbon)
20% 20%
Others Others

Fig. 3.22

ROLE OF COMPONENTS IN VISO

Component Advantage Disadvantage

ALUMINA Resists molten steel. Attacked by mould flux (Basic and Acidic).
Thermal Shock.
ZIRCONIA Resists steel and mould Attacked by mould flux (Basic and Acidic).
flux better than alumina Thermal Shock.
MAGNESIA Resists steel and basic Attacked by acidic mould flux.
mould flux Thermal Shock.
GRAPHITE Thermal shock resistance Oxidizes above 650°C.
Not wetted by mould flux. Dissolves in steel.
SILICA Thermal shock resistance. Attacked by basic mould flux, steel.
CARBON BOND Not wetted by mould flux. Oxidizes above 400°C. Dissolves in steel.
ADDITIVES Reduce carbon and Decrease Refractoriness.
graphite oxidation. Increase erosion in steel and mould flux.
Thermal Shock.
EXTERNAL GLAZE Protects carbon and graphite Dissolves in steel and mould flux.
from oxidation.
Table 3.4 showing role of components in VISO products

Chp. 3 17
 40

1.0 35
12345
0.93
12345
12345 30
12345
12345
0.8
12345
12345 25

% ERODED TUBES
12345
12345
Index of wearing rate

12345 20
12345
12345
0.6
12345
12345 15
12345
12345
12345 10
12345
12345
12345
12345 5
0.4
12345
12345
12345
12345 0
12345 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5
12345
12345
0.2 0.11 0.12 0.11 12345 % Mn
0.08 0.09 12345
0.07 12345
12345 Fig 3.25 Relation between fraction of eroded pouring tubes
12345
0
12345 and Mn content in steel at 1550°C to 1560°C for a steel
containing 0.2 to 0.25% Si.
Seamless wire rod rail heavy electrical Hot Coil High
Pipe plate sheet oxygenised
steel
submerged nozzle results in gradual
Fig 3.23 Comparison of index of wearing rate
external erosion of that part of the nozzle.
for each steel grade
Higher the speed of a continuous caster is
lower the viscosity and the melting point of
1.0 the mould powder.
[0] content required to
High-Oxygenised steel. Figs 3.27 and 3.28 show the relationship
between the viscosity and the flourine
0.8 content of mould powders on the erosion of
zirconia graphite refractories.
Index of wearing rate

In table 3.4 the behaviour of some materials

0.6
in relationship to slags and metals is shown.

PROTECTION FROM OXIDATION

0.4

0.2 WATER-COOLED
SUBMERGED
COPPER MOULD MOULD
NOZZLE
POWDER
0
50 100 150 200 250 CARBON
Free [0] content in molten steel [ppm] FLUX ENRICHED

Fig 3.24 Relation between free (O) content in molten steel MOLTEN
and index of wearing rate FLUX

- to protect the steel from oxidation by the

atmosphere SOLIDIFIED
FLUX
- to create a molten slag having two SHELL
purposes, one to lubricate the mould and
LIQUID
the other to effect a good thermal
STEEL
transfer between the solidifying steel and
the mould surface.
Fig. 3.26 shows the cross section through a
continuous casting mould.
OSCILLATION
The components of mould powders depends MARK
on supplier know-how and application. The STRAND
WITHDRAWAL
action of the molten mould powder on the
Fig 3.26
Chp. 3 18
The graphitized carbon bonded materials This protection can be achieved with two
exhibit exceptional properties which meet approaches:
the requirements necessary to manufacture
- inside the body of the mix
refractories for continuous casting
- on the surface of the finished product
operations. There is one disadvantage of this
The first, to protect from oxidation each single
material which needs to be prevented:
graphite flake and the glassy ribbons of curly
Both graphite and carbon bond are very carbon; the second to protect the final
susceptible to oxidation. product during preheating and casting.
From the thermogravimetric analysis (see Fig.

10.0

0
8.0
Bond
2 Graphite
Erosion (mm) per 1Hr

6.0

Incremental Weight Loss %120°C

Carbon bonded
4
4.0

0
2.0
Graphite
2
0
1.0 2.0 3.0 5.0 7.0 10.0
4
Viscosity (Poise) at 1300°C Ceramic bonded

Fig 3.27 Relationship between viscosity of mould powders 6

and erosion of zirconia graphite refractories.

200 600 1,000 1,400

10.0 Temperature °C

8.0 Fig 3.29 Thermogravlmetric analysis of carbon versus

ceramic-bonded alumina graphite
Erosion (mm) per 1Hr

6.0
4.0
2.0
0 and generates a glassy phase which coats
2 4
[F°]
Fig 3.28 Relationship between F- content of mould powders
and erosion of zirconia graphite refractories.
3.29) it is possible to see that the range of
temperature at which maximum oxidation
occurs is from 350°C to 800°C.
It is interesting to note that the carbon bond
burns off at a much lower temperature than
graphite.
If the carbon bond and the graphite are
oxidised, there is a collapse of the properties
of the material. It is therefore necessary to
protect them both from oxidation.
PROTECTION OF THE BODY OF THE MIX
This protection is achieved through two
different additions:
- the so called body glaze (B203)
- precursors
The body glaze: B2O3 has a low melting point
6 8 10 the graphite and the carbon bonding so
(wt%) protecting the body from oxidation.
The precursors are oxygen getters. This
means that their activity with O2 is higher than
that of graphite and the carbon bond. The
most used precursors are;
Silicon metal : Si
Silicon Carbide : SiC
Silicon in presence of oxygen gives rise to
the following chemical reaction:
Si + O2 = SiO2
- the product is a silica-rich glassy phase
which blocks the pore structure and
slows the rate at which the oxygen can
further penetrate the structure.
Chp. 3 19
 Fig 3.30

Silican carbide reacts with oxygen according glaze will flow off the piece the strength of
to the following formula: the flame should be limited together with the
preheating time (see Fig. 3.31)
2 SiC + 302 = 2SiO2 + 2CO
2 CO + O2 = 2CO2 To correctly achieve a good glassy phase of
Once again we have a silica rich glassy phase the glaze it is necessary to have a slightly
operating in the same way as for silicon oxidising flame from the burners used for the
metal and additionally a further reaction of preheating.
CO with Oxygen that increases the activity
The composition of a glaze is defined
of SiC as oxygen getter.
according to:
PROTECTION OF THE SURFACE OF THE PRODUCT - The desired melting point and range of
Oxidation of graphite and carbon bond temperature of protection.
happens through the surface of the product - The surface properties of the material to
during the firing of the product itself (stopper protect.
rods and ladle shroud) and during the - The thermal expansion of the material
preheating (submerged nozzle - stopper rod) to protect.
and during casting (all the patterns) - - The viscosity of the liquid glassy phase.
Following these principles Vesuvius have
The protection from this oxidation is ensured
developed and use different types of glaze:
by glazes whose purpose is to create an air
the most used are
proof barrier to oxygen as shown in Fig. 3.30.
G 74 G 40 G 95
THE GLAZE
The glaze, externally applied to products with GLAZE
Inefficient glaze
a thickness less than 1mm, is a ceramic
material composed of several compounds Softening & Beginning Glaze becomes liquid and
that in certain conditions of temperature and of melting dripping may occur
oxidising atmosphere, will react to form a Blown away by burners
liquid glassy phase which protects the
Efficiency

material from oxidation.

The glaze is only protective once the melting Glaze is
point (from 800 to 1000°C) has been reached. washed
The best protection is obtained when the
viscosity of the glassy phase is low enough
to leave a good coating on the surface to
protect. Maximum efficiency T°
T°1 T°2
Since the glaze viscosity decreases as Adequate viscosity -> protection
temperature increases and to avoid that Fig 3.31

Chp. 3 20
 G74 G40 G95

Application Ladle Shroud Submerged Entry Shroud Newly

Stopper Rod Submerged Entry Nozzle Developed

Chemistry (Wt%) non oxide and metallic phases converted to oxide percentages

SiO2 66.5 66.4 71.8

B2O3 11.4 11.3 7.3
Al2O3 8.4 8.4 12.1
K2O 1.9 1.9 1.2
Na2O 8.2 8.2 5.2
Fe2O3 0.2 0.2 ---
Others 3.4 3.6 2.4

Softening Termperature 720°C 760°C

Melting Temperature 740°C 815°C 800°C
Effective Use Temperature 750-1200°C 825-1400°C 815-1400°C
Recommended Use Temperature 900-1100°C 950-1200°C

Table 3.5

The composition of these glazes are shown PREHEATING OF ALUMINA GRAPHITE

in Table 3.5. MATERIALS
Ladle shrouds and stoppers are shipped to We have seen from the graph showing the
the customer with vitrified glaze which incremental weight loss as a function of
appears on the pattern as a black shiny temperature that the oxidation of carbon
material, which is resistant to abrasion and bonded material starts at about 350°C and
does not dissolve in water. remains important until about 800°C.
Subentry nozzles and shrouds are normally Since subentry nozzles and shrouds have
shipped to the customer with unvitrified glaze green glaze applied and therefore in that
usually called green or raw glaze. The green range of temperature are not protected by
glaze appears as a dull grey chalky material the glaze it is necessary to preheat through
which is susceptible to abrasion and that temperature range very quickly.
chipping. At this green stage the glaze does
not protect the product from oxidation and PREHEATING CURVE
is dissolved by water. The correct preheating curve for carbon
Table 3.6 shows a list of glazes used in bonded refractories is shown in Fig. 3.32. It
Vesuvius and developed for special can be seen that preheating in the range
applications. 350-800°C should be done as fast as
possible to avoid oxidation of the carbon
G40 Standard glaze for subentry nozzle bonding and graphite. At 800°C the green
and shrouds glaze matures and from that point is
G74 Standard glaze for stoppers and ladle protecting the carbon bonded material.
shrouds
G19 Low temperature glaze for low
preheating temperature
G29 Glaze for subentry nozzles and
shrouds for mixes sensitive to
oxidation
G34 Higher range of protection for standard
mixes
G95 High temperature protection for
subentry nozzles and shrouds
G96 Glaze for high temperature and long
preheat times (stopper nose)
G97 Glaze for materials sensitive to
oxidation (MgO stopper nose)

Chp. 3 21
 Chemistry G40 G74 G19 G29 G34 G95 G96 G97

SiO2 66.4 66.5 64.6 65.7 66.5 71.8 66.0 65.8

Al2O3 8.4 8.4 8.1 8.3 8.4 12.1 8.3 8.3

Na2O 8.2 8.2 8.1 8.2 8.2 5.2 8.2 8.2

K2O 1.9 1.9 1.9 1.9 1.9 1.2 1.9 1.9

B2O3 11.3 11.4 11.0 11.2 11.4 7.3 11.3 11.3

CaO 1.0 1.0 1.1 1.0 1.0 0.6 1.0 1.0

MgO 0.2 0.2 0.2 0.2 0.2 0.1 0.2 0.2

Fe2O3 0.2 0.2 0.3 0.2 0.2 0.1 0.2 0.2

ZrO2 0.1 0.1 0.1 0.1 0.1 0 0.1 0.1

LiO2 0 0 3.0 1.1 0 0 0.7 1.1

Other 1.7 1.7 1.7 1.7 1.7 1.1 1.7 1.7

LOI 0.6 0.3 0.3 0.5 0.5 0.4 0.4 0.3

TEMP
RANGE 850 800 725 750 800 850 750 750
OF USE 1250 1250 1050 1250 1300 1550 1300 1200
°C

Table 3.6

TEMP °C PREHEATING CURVE - Recommended for Alumina Graphite

1,400

1,200 CRACKS GENERATION CAUSED BY MODIFICATION OF MATERIAL

INTERNAL STRUCTURE

1,000 OXIDATION CAUSED BY

TEMPERATURE SCALE °C

TOO LONG PREHEATING

800 CRACKS GENERATION CAUSED BY TOO LOW PREHEATING TEMPERATURE

600

400

200

0
0 10 20 30 40 50 60 70 80 90 100 110 120
TIME (MIN)
Fig. 3.32

Chp. 3 22