Refractories 01
Refractories 01
Refractories 01
Hussein Alaa
Introduction to Refractories
Refractories are material having high melting points, with properties that
make them suitable to act as heat-resisting barriers between high and low
temperature zones.
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Refractories by: Dr. Hussein Alaa
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Refractories by: Dr. Hussein Alaa
Classification of Refractories
Refractories are classified into number of ways on the basis of chemical
properties of their constituent substances, their refractoriness, method of
manufacture and physical form.
Acid Refractories:
Acid refractories are those which are attacked by alkalis (basic slags).
These are used in areas where slag and atmosphere are acidic. Examples of
acid refractories are:
1) Silica (SiO2).
2) Zirconia (ZrO2).
3) Aluminosilicate.
Neutral Refractories:
Neutral Refractories are chemically stable to both acids and bases and are
used in areas where slag and atmosphere are either acidic or basic. The
common examples of these materials are:
1) Carbon graphite (most inert)
2) Chromites (Cr2O3)
3) Alumina
Out of these graphite is the least reactive and is extensively used in
metallurgical furnaces where the process of oxidation can be controlled.
Basic Refractories:
Basic refractories are those which are attacked by acid slags but stable to
alkaline slags, dusts and fumes at elevated temperatures. Since they do not
react with alkaline slags, these refractories are of considerable importance
for furnace linings where the environment is alkaline; for example non-
ferrous metallurgical operations. The most important basic raw materials are:
1) Magnesia (MgO) - caustic, sintered and fused magnesia
2) Dolomite (CaO.MgO) - sintered and fused dolomite
3) Chromite -main part of chrome ore
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Shaped Refractories:
Shaped refractories are those which have fixed shaped when delivered to
the user. These are what we call bricks. Brick shapes may be divided into
two: standard shapes and special shapes.
Standards shapes have dimension that are conformed to by most
refractory manufacturers and are generally applicable to kilns and furnaces
of the same type.
Special shapes are specifically made for particular kilns and furnaces.
This may not be applicable to another furnaces or kiln of the same type.
Shaped refractories are almost always machine-pressed, thus, high
uniformity in properties are expected. Special shapes are most often hand-
molded and are expected to exhibit slight variations in properties.
Unshaped Refractories:
Unshaped refractories are without definite form and are only given shape
upon application. It forms joint less lining and are better known as
monolithic refractories. These are categorized as Plastic refractories,
ramming mixes, castables, gunning mixes, fettling mixes and mortars.
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Refractories by: Dr. Hussein Alaa
Properties of Refractories
Important properties of refractories are: chemical composition, bulk
density, apparent porosity, specific gravity and strength at atmospheric
temperatures. These properties are often among those which are used as
control points in the manufacturing and quality control process.
1) Melting Point:
MELTING
REFRACTORY ELEMENT
TEMPERATURES (C)
Graphite C Pure 3482
Thoria, ThO2 Pure Sintered 3000
Magnesia, MgO, Pure Sintered 2800
Zirconia, ZrO2 , Pure Sintered 2700
Lime, CaO 2570
Beryllia, BeO, Pure Sintered 2550
Silicon Carbide, SiC, Pure 2250
Magnesia, 90-95% 2193
Chromite, FeO-Cr2O3 2182
Chromium Oxide 2138
Alumina, Al2O3, Pure Sintered 2050
Chromite, 38%, Cr2O3 1970
Fireclay 1870
Titania, TiO2 1850
Kaolin 1816
Silica, SiO2 1716
The melting point serves as a sufficient basis for considering the thermal
stability of refractory mixtures and is an important characteristic indicating
the maximum temperature of use.
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Refractories by: Dr. Hussein Alaa
more porous materials are usually used for thermal backup. Refractory
materials with high porosity are usually NOT chosen when they will be in
contact with molten slag because they cannot be penetrated as easily.
- Thermal conductivity decreases because the air which fills the pores acts
as an insulator, which is why insulating bricks have higher porosity.
- Resistance to the penetration of metal, molten slag and flue gases
reduces due to increased permeability.
- Temperature fluctuation sensitivity reduces as pores can accommodate
the thermal expansion due to heat.
- Strength reduces due to decreased compactness obviating their usage in
taller structure demanding higher strength.
Porosity determination:
In raw/green refractory materials the pores are all open fluids can pass
through them. When these materials are fired some liquid formation due to
fusion takes place and as a result some pores will be sealed. The apparent
porosity as such takes the open pores and not the closed pores. True porosity
is defined as:
The total porosity present can be found by relating the theoretical density
(th), to the calculated density (). The total porosity (T.P) of the sintered
samples is also calculated from the following equation:
4) Density:
True density is the weight per unit volume of the refractory including the
volume of its open and close pore space.
The specimen is then boiled in deionized water for more than 1 hour and
cooled to room temperature. The immersed weight in deionized water (S) is
measured at room temperature. The test specimen is then lifted up slowly
from the immersion liquid by means of the sling thread. Saturated weight
(W) of the test specimen is found by weighing the soaked specimen (after
wiping off the liquid droplets from the specimen surface by a blotting paper)
while suspended in air. The bulk density is then calculated by:
This is one of the main criterias for assessing the quality aspect of the
particular brick. The true specific gravity of the material composing a brick
as distinct from the bulk density of the brick as a whole (including the pore
spaces) is of special significance only for silica bricks and magnesite bricks.
This is due to almost constant composition of other bricks.
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5) Refractoriness
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The standard cones are called 'Segar cones' (as Germany standard) and
'Orton cones' (as British standard) and they are numbered according to their
refractoriness/fusion points. Average refractoriness values of some
refractory bricks are given in Table (2). PCE can be useful for quality
control purposes to detect variations in batch chemistry that result from
changes or errors in the raw material formulation.
Figure (1)
Table (2)
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The refractoriness under load test (RUL test) gives an indication of the
temperature at which the bricks will collapse, in service conditions with
similar load.
Refractory failure is also influenced by its exposure time to load and heat.
Longer exposure time results in failure of refractory under relatively low
load and temperature conditions. Similarly refractories will fail at a lower
temperature with increased load.
8) Strengths:
Cold and hot, their importanceThe physical strengths, in both cold and
hot conditions, are often characterized as measures of the use of a refractory.
Cold strengths indicate the handling and installation of the refractory,
whereas hot strengths indicate how the refractory will perform when used at
elevated temperatures. Initial strength develops in refractory materials
during the forming process. For shaped refractories, the strengths often
develop during the physical processing of the products and sometimes
followed by higher temperatures where the refractory goes through a firing
process. For monolithic refractories, the initial strength develops during the
installation or forming process (for precast shapes), and the final strength
develops while in application.
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( ) ( )
( ) ( )
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9) Thermal Properties:
a) Thermal Conductivity:
Increasing the heat capacity; increasing the number of carriers and their
velocity and increasing the mean free path (decreasing scattering) result I
increased thermal conductivity.
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b) Thermal Diffusivity
Where:
c) Thermal Expansion
L = L0 T
Where:
: the Coefficient of linear expansion.
L0: Initial length of the object.
L: Length change of the object.
T: Temperature change of the object.
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Refractories by: Dr. Hussein Alaa
A = A0 T
Where:
: the Coefficient of Area expansion.
A0: Initial area of the object.
A: Area change of the object.
T: Temperature change of the object.
V = V0 T
Where:
: the Coefficient of volume expansion
V0: Initial volume of the object
V: Volume change of the object
T: Temperature change of the object.
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d) Thermal Shock
( )
Equation (1) indicates that the thermal stress increases as the elastic
modulus and thermal expansion coefficient of the refractories increases. The
temperature difference ( ) can be decreased by increasing the thermal
conductivity of the refractories.
( )
( )
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Refractories by: Dr. Hussein Alaa
Where: : The symbol stands for the strength of the ceramic material.
As ceramic materials subjected to thermal shock generally fail in tension
rather than in shear or compression, the tensile strength is generally used as
the criterion for failure rather than the compressive or shear strength. As the
thermal shock resistance of a ceramic material is governed mainly by its
mechanical and thermal properties, as indicated above, an improvement of
the thermal shock resistance of the high Young's modulus of ceramics.
e) Thermal Spalling
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