REFRACTORY SCIENCE

REFRACTORIES - materials that possess a high degree of resistance to

fusion; materials suitable for use in furnace construction

The diversity of furnace service conditions may require different properties of

refractories at the following different applications:

 infusibility at extreme temperature

 resistance to slag attack
 compressive strength at high temperature
 resistance to abrasion and dust erosion
 high thermal conductivity for some applications

The proper choice and use of refractory materials is vital to the success or failure
of a process.

1.0 Properties of Refractories

It is through skill and judgment of the engineer by which refractories are selected
according to its properties suitable for the service conditions. The different
refractory properties are as follows:

1.1 Composition and Structure

The composition and structure of the refractory determines the important service
and physical properties of the refractory. Composition is expressed by giving the
chemical analysis in percentage of the component oxides such as % SiO2, % MgO,
% Al2O3, % FeO, etc. Composition of the refractory is the basis for classifying
them as acidic, basic or neutral. Small amounts of impurities seriously affect the
service property under extreme furnace conditions.

The structure of the refractory involves solid grains and crystals of the refractory
materials in a matrix or ground mass. The matrix may be glass, finely crystalline
mass, or a mixture, which acts as the cement or bond of grains of refractory
materials. The matrix does not entirely fill the space between refractory grains, so
that the structure as a whole is porous. The formation of the bond is generally
accomplished by firing or heating to a temperature high enough to form liquid of
the bonding constituents. When the body is cooled, the liquid may simply become
glassy or it may crystallize. This ground mass of a refractory body is the less
refractory portion of the structure and is the portion where liquid formation occurs
first in service at high temperature.

Equilibrium diagrams are essential tools in interpreting and predicting structures

of refractory bodies and structural changes during firing and service. They show
important relationships between composition and melting point. Further,
microscopic studies are also vital tools in determining valuable information which
may facilitate the diagnosis of refractory failures.

1.2 Service Properties

1.2.1 Fusion and Softening Temperature

Fusion is the melting of a material from solid to liquid while softening is the
tendency of a material to collapse.

Fusion and softening temperature is the first in the list of service properties since it
is the requirement of a refractory material to withstand high temperature. As what
refractoriness is defined, it is the ability of a material to withstand high
temperature. Once the material fails in this property, all other properties fail since
fusion and softening will be the cause of spalling, failure to load bearing, etc.
Refractories should be selected such that they have fusion and softening
temperature way above the furnace temperature.

Fusion and softening temperature is determined by the PCE - Pyrometric Cone

Equivalent Test or the ASTM Test C-24. In the test, the sample is pulverized to
minus 65 mesh and then formed into a test cone as shown in the diagram. Water
and small amount of dextrin or glue are added to act as binders in making the
cones. These cones are mounted on an inert plaque with a series of Standard
Pyrometric Cones. It is then heated at a specified rate in a furnace with uniform
distribution of temperature. Softening of a cone is indicated when the cone bend
down until it touches the plaque. The PCE corresponds to the number of the
Standard Pyrometric Cone which nearly corresponds in time of softening
temperature to the test cone.

1.2.2 Resistance to Chemical Attack

Chemical attack is the reaction of the slag, and dust-laden gases to the refractories.
It is very rare to find a refractory which is not resistant to slag. Hence, it is a
practice to select a refractory which has the highest resistance to slag.

It is common practice to use refractories which are insoluble to the slag. However,
it is rarely possible to find a refractory which is insoluble in the slag. Hence, the
solution is to minimize the rate of attack. Acid slags will require acid refractory
while a basic slag will require basic refractory. A neutral refractory can be used
for both an acid and a basic slag.

When a slag remains in contact with the refractory wall, a liquid zone is formed
between the refractory and the slag. This zone has the higher melting point and
higher viscosity than the slag and acts as a barrier between the slag and the

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refractory. This barrier will be retained at the surface and will be deterrent to
rapid slag-refractory reaction.

Erosion by dust-laden gases is accelerated by reactions between the dust and the
refractory. Joints between dissimilar refractories may have reactions and in some
cases due to action of carbon monoxide decomposing to carbon.

No simple laboratory tests have been developed to measure the rate of slag
erosion.

1.2.3 Expansion and Shrinkage

Expansion and shrinkages are very important properties in refractories since these
lead to volume changes of the brick. These volume changes in turn result to
failure of the brick and the furnace as a whole during operation. The expansion
and shrinkage of the refractory are measured by the coefficient of thermal
expansion. The volume changes are caused by allotropic changes in solids
associated in the structure and phase constitution of the body. An example is the
expansion occurring when quartz transforms to either tridymite (17.2% increase in
volume) or to cristoballite (14.3% increase in volume).

Expansion and shrinkage in the refractory may be reversible or irreversible. This

is very much dependent on the firing temperature of a brick. This firing completes
the irreversible and permanent volume changes. The greater the firing
temperature, the greater is the irreversible shrinkage. The change is associated
with the formation of glass and liquid which pulls the structure together.

This property is determined by ASTM Test C-113 or known as the ”Reheat

Change of Refractory Brick”. The test includes specific heating schedules for
different types of refractories and the change is reported as a percentage change in
length.

Knowing the coefficient of thermal expansion, allowances should be allotted

between refractories in order to give room for volume changes during extreme
furnace condition.

1.2.4 Spalling

Spalling involves the fragmentation and fracture occurring in the hot surface area
such that fragments are lost and progressively exposing new surface. Spalling
resistance is a function of refractory composition, structure and constitution.
Spalling is of three (3) kinds namely:

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 Mechanical spalling - resulting from improper design of brick walls. No
allowance for thermal expansion was allotted
wherein some parts of the wall may be overloaded
and thus tend to fracture.

Thermal Spalling - caused by the stresses due to temperature gradients

from the inside and outside of the brick. Example is
the volume change on heating and cooling when
passing at allotropic change.

Structural Spalling - due to change in brick structure in zones extending

only partway into the brick. This may be caused
chemical alterations due to impurities.

Spalling is determined by ASTM Test C-38 wherein it consists of heating and

rapidly cooling test panels through a fixed number of cycles, then determining the
weight loss by spalling as a measure of spalling resistance.

1.2.5 Load Bearing Capacity

Load Bearing capacity is the property of a refractory material for a roof arch
which is supported by a constant compressive force applied to the sides. Failure
under load is related to:

- Softening temperature - the load bearing capacity has become so small

that it deforms under its own weight.
- Expansion and shrinkage
- Spalling resistance

ASTM Test C-16 involves heating the test specimen according to a fixed time
temperature schedule under a compressive load of 25 psi. The lengths of the
specimen are measured at room temperature before and after heating, and the
deformation is expressed as per cent of the original length.

1.2.6 Abrasion Resistance and Mechanical Toughness

This is provided in furnace parts which are continuously or frequently in contact

with moving solid materials or objects. The abrasive actions may include
scraping, scouring, rubbing, or impingement of fine particles. The best example is
the refractory in the refractory in the rotary kiln.

There is no generally accepted quantitative measure of this property which may be

determined in a laboratory test.

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1.3 Other Physical Properties

1.3.1 Thermal Conductivity

Thermal conductivity is the property of material to transmit heat. Different

applications require refractories with different thermal conducting properties.
Internally heated furnace require refractories with low thermal conductivity in
order to retain the heat inside while externally heated furnaces require higher
thermal conductivity for the heat to enter the heating portion at a shorter time.

This property is measured by ASTM Test C-201. The test measures the thermal
conductivity of a material.

1.3.2 Cold Crushing Strength and Modulus of Rupture

These property indicates how a brick can withstand handling, shipping and
mechanical loading at low temperature. It is also a measure of ceramic bond
strength developed in firing and sometimes may be correlated with certain
structure-sensitive service characteristics of the brick. This property is measured
by ASTM Test C-133.

1.3.3 Bulk Density

It is the weight divided by total volume including pores. True specific gravity or
true density refers to the solid refractory, exclusive of pores. Apparent specific
gravity is measured by immersion in a fluid which penetrates the open pores of the
body, and thus, refers to the solid refractory including closed pores. Porosity and
apparent porosity (open pores) are readily calculated from these specific gravities.
Standard procedures for measurement and calculation are given in ASTM Tests C-
134 and C-135.

1.3.4 Heat Capacity and Specific Heat

1.3.5 Electrical Conductivity

Best for materials used in electric furnace. Silicon carbide and graphite are good
heating elements.

1.4 Costs

Materials, fabrication, maintenance , indirect and other charges

Specific properties of more costly materials justify their uses.

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2.0 Manufacture of Refractories

2.1 RAW MATERIALS

 mineral deposits – clays, sands, ores, rocks
 mined, quarried and then crushed

Manufacturing Process

2.2 CRUSHING
 carried out in a simple crushing equipment
 materials are graded and stored by size

2.3 BLENDING
 Composition of the brisk is adjusted by blending the materials along with
any flux or bond additives
 In most cases, there is only one mineral used with appropriate bonds added
 Not only by composition but also by size which attribute to the properties
of the product
 Low porosity can be attained by “close-packing grading”
 Interstices between the largest particles are filled by smaller grade, and
the residual interstices filled by smaller grade again and so ad infinitum
 There is some control on the ultimate porosity
 The strength is also high since there is maximum number of contacts of
materials
 Carried out in a paddle mill with a kneading action
 Water and bonds area added
 Clays attain plasticity at this stage

MOULDING
 Standard shapes are machine moulded
 Non-standard shapes are hand moulded

 Hand Moulding
 Most successful with plastic mixes usually rather wet (14-20% water)
 Mixes can be “thrown” into the wooden box-type mould and relied on
to fill it
 Cheaper than machine moulding on a jobbing basis
 Machine moulding is preferred for mass production

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  Semi-plastic machine-moulding
 Undertaken on mixes with about 10-12% water
 Uses moderate moulding pressures
 Two-stage process-extrusion to a rough shape followed by pressing to
an exact shape

 Dry-press method
 Used for all non-plastic basic mixes as well as clays with not more than
5% water
 Fine spray or mist is used since addition of so little water is not easy
 High pressure in the order of 350-1400 bar is applied in the mould thus
trapping air
 Clay may be de-aired by vacuum treatment before moulding or by using
vacuum blocks in the mould wall.
 Green strength is low thus it is difficult to maintain good edges and
corners

 Slip-casting
 Applicable only to clays which can be formed into a colloidal
suspension with water
 Poured into a mould of Plaster of Paris which absorbs the water and
causes a uniform deposit of clay to build up in the inside of the mould
 Most useful for awkward shapes and for hollow ware
 Used for special refractories which are prepared from very fine
powders

DRYING
 in large drying floors (heated by waste heat from kilns) where the bricks are
laid out in open array
 in tunnel kilns
 where they are stacked on bogeys and passed through a tunnel against a
stream of hot air
 faster and more compact but cannot be adopted where sizes and shapes
are not constant

FIRING
 Beehive oven
 The traditional furnace
 In some cases, there are a large number of kilns side by side
 The firing kiln at any time is heated by a fire of coal or coke using air
preheated by being drawn through several cooling kilns

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  The combustion products are passed over bricks in several preheating
kilns before passing to the stack
 Heating must be uniform in each kiln so that the bricks attain a uniform
temperature before the fire is advanced to the next compartment

 Tunnel kiln
 Firing zone is of oil burners in the middle of its length
 Cold secondary air is pre-heated as it cools the fired bricks on their way
out
 Combustion gases preheat the advancing cold bricks
 Heating cycle and time at top temperature are important and may vary
from one type of brick to another
 Firing temperature should be as high as that at which the brick is to be
used to ensure completion of reactions and sustain a high a degree of
dimensional stability as is practicable

SPECIAL REFRACTORIES

Laboratory Alumino-Silicates
 Porcelains and mullites are obtained in tube and crucibles form
 Service temperatures ranging from 1200oC to 1650oC

Laboratory Silica
 Available as vitreosil – a pure silica, fused and drawn out to tube form and
worked like glass into crucibles, dishes and other shapes
 Normally translucent, but it can be obtained clear like glass
 Very low coefficient of thermal expansion- almost zero
 Very resistant to thermal shock
 Can be used up to 1100oC to 1200oC

Beryllia (BeO)
 Melting point is 2550oC
 Sublimes above 2000oC and also reacts with small amounts of water vapor
to form volatile hydroxide above 1650oC
 Strong at low temperatures
 Good thermal shock resistance
 High thermal conductivity
 Very unreactive chemically with metals and carbon, including alkalies,
alkaline earths, rare earths, uranium,

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Thoria (ThO2)
 Melts at about 3300oC
 Occurs along with rare earths and its purification renders it expensive
 A basic refractory, reacting with silica but not with basic slags
 Poor thermal shock resistance
 Radioactive
 Used as a crucible for pure metals since interaction is slight

Zirconia (ZrO2)
 Melts at 2677oC
 Oxide is an acid and reacts with basic oxides and slags
 Stable to both oxidizing and reducing atmosphere up to 2200oC
 Poor spalling resistance
 Low thermal conductivity making it as a good high temperature insulator
 Unreactive towards metals
 Good electrical conductor at high temperatures

Zircon (ZrSiO4)
 Melts at 2420oC
 Acid refractory
 Dissociates to zirconia and glass at 1750oC
 Low thermal expansion
 Good spalling resistance

METALLURGICAL BRICKS/FURNACE CONSTRUCTION

Bricks, blocks and other shapes

 The standard brick used is the “9-inch straight” with a dimension of 9 x 4 ½
x 2 ½ inches
 Many other sizes and shapes primarily for single kind of furnace, such as
cupola blocks, blast furnace blocks, rotary-kiln blocks, etc.

Mortar and Cements

 Used to from the joints in laying brickwork
 Purchased dry and mixed with water to attain proper consistency before use
 The “batter” is applied by toweling, dipping or pouring
 Two types:
o hot-setting – forms strong bond only after firing, and make a
cement bond essentially similar to that developed in firing a brick

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 o air-setting – contains sodium silicate which develop a strong
bond and impart a set merely on drying at room temperature; a
ceramic bond is developed when heated

Plastics, ramming mixtures and castables

 Materials used to form the desired shape in place
 Mixed with water and then rammed into place and into the
desired shape in the cold furnace
 Air-setting bond is added to gain strength at low
temperatures
 Castables are mixed and poured like concrete and thus are
also called as refractory concrete

2.0 Types of Refractory Bricks

There are three (3) classifications of refractory materials in terms of usage and
composition:

Acidic - SiO2, SiO2-Al2O3

Basic - CaO, MgO, Al2O3
Neutral - Al2O3·SiO2, Cr2O3, non-oxide like C and SiC

2.1 Acidic Refractories

2.1.1 Silica brick and Other High Silica Refractories

 Manufactured from sandstone and quartzites that contain entirely SiO2.

 Cheap, good mechanical strength, fusion temperature at 3200 oF.
 Good load bearing capacity, lightweight, constancy of volume at high
temperature.
 Not suitable for intermittent operation since it is sensitive to structural
spalling at 1200 oF.
 Immune to spalling above 1200 oF.
 Low bulk density and high thermal conductivity

2.1.2 Siliceous-Alumina Refractories

 These refractories are based on the SiO2-Al2O3 system, wherein this ranges
from pure SiO2 to high Al2O3. However, a 5.5% Al2O3 in the refractory is

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 very disadvantageous since this is a eutectic and has a lower melting point
than SiO2.
 Refractoriness of SiO2-Al2O3 bricks increase with alumina content over the
entire composition range from the eutectic with only 5.5% Al2O3.

2.2 Basic Refractories

2.2.1 Alumina Refractories (50% to 80% Al2O3)

 Manufactured from diaspore (Al2O3·H2O) and gibbsite (Al2O3·3H2O)

 Good resistance to slag attack especially high in lead oxide, alkali-metal
oxide.
 Good load bearing capacity at high temperature.

2.2.2 Magnesia

 Made by calcining magnesite (MgCO3) or brucite (MgO·H2O).

 Considered as the most basic refractory material.
 Very high fusion temperature (2800 oC/5070 oF)
 Low spalling resistance to sudden temperature changes.
 High density, high coefficient of thermal expansion.
 Poor load-bearing ability at high temperature.

2.2.3 Lime (CaO)

 High melting point (2570 oC/4460 oF)

 Slakes readily with water and air forming hydroxide and carbonates.

2.2.4 Dolomite (CaO·MgO)

 Used in large quantities as a basic refractory, especially in maintaining the

bottoms and banks of basic-open hearth furnace

2.3 Neutral Refractories

2.3.1 Fireclay and Firebricks - Al2O3·2SiO2·H2O (21% to 43% Al2O3)

 Principal constituent is kaolinite (Al2O3·2SiO2·H2O)

 Contains aluminous silicates with small amounts of oxides such as CaO,
MgO, FeO.
 Cheapest and most widely used.
 Maintains their strength at high temperatures.

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  Resistant to low thermal spalling.
 Good degree of refractoriness when fired.

2.3.2 Chrome (Cr2O3)

 Made from high-grade chromium spinel ore (Fe,Mg)O·(Cr,Al,Fe)2O3

 Used to separate acid from basic refractories
 Lower cost than magnesite
 Melts at 3960 oF.
 Low thermal conductivity.

2.4 Special Refractories

2.4.1 Graphite

 Vaporizes at 3600 oC.

 Reacts with oxygen and metal oxides even at 700 oC forming CO and
CO2.
 Good electrical and thermal conductivity
 High refractoriness

2.4.2 Silicon Carbide - Carborundum (SiC)

 Does not fuse or soften at any temperature.

 Decomposes C to CO2 and Si by volatilization at 1650 oC to 1300 oC
(3000 oF - 2370 oF).
 High thermal and electrical conductivity.
 Good mechanical properties such as abrasion resistance, etc.

3.0 Refractories in Furnaces

3.1 Blast Furnace

 Stack and Bosh Lining - fireclay

 Hearth and Crucible - super duty fireclay with carbon lining

3.2 Cupola
 Stack - hard burnt fireclay
 Hearth - Acid - fire brick and silica
Basic - magnesite, chrome-magnesite, or burnt dolomite
- carbon lining

3.3 Electric Arc Furnace

Acidic

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  roof and side walls are silica brick
 hearth has a first layer of fire bricks next to the shell, followed by two (2)
courses of silica bricks, finely rammed with hearth mixture silica sand

Basic
 roof is constructed either of silica brick or sillimanite

 outer circle is made of chrome magnesite and side walls are lined with
silica bricks or magnesite or chrome-magnesite
 hearth shell - magnesite, dolomite and rammed with magnesite or
dolomite powder.

3.4 Induction Furnace

 Acid - rammed ganister bonded with clay or sodium silicate
 Basic - sintered magnesite, fused alumina or zirconia

3.5 Basic Open Hearth Furnace

 Hearth - dead burned magnesite on a magnesite or chrome brick
- magnesite or chrome bricks are used for areas in contact with
slag
 Magnesite bricks are used for suspended roofs and silica bricks are used
for arches.

3.6 Basic Thomas Converter

 Magnesite fused alumina

3.7 LD Converter (Basic Oxygen Process)

 single layer of burnt magnesite brick rammed with a basic mix

 usually lined with tar-bonded dolomite or magnesite buck

3.8 Ladle
 Fireclay or firebrick

3.9 Crucible
 Silicon carbide or graphite

3.10 Reverberatory Furnace

 Hearth - consists of silica sand rammed with binder or burned grain
magnesite and slag
 Walls - constructed with magnesite brick backed-up with silica brick
 Roof - made of silica brick

4.0 Heat Transfer in Refractories

K A T

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 q = ------------
x

T = driving force
= -------------
x/ KA = resistance

where: K - thermal conductivity (btu/ft-hr-oF or btu-in/ft2-hr-oF)

q - heat transferred (btu/hr)
A - area (ft2)
x - thickness (ft, in)
T - change in temperature (oF)

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