Refractory

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 Contents
 What are Refractories
 Refractory Industry Overview
 Role of Refractories
 Properties of Refractories
 Classifications
 Manufacturing Process
 Aspects of Phase Diagram in Refractory Technology
 SiO2-Al2O3 Phase Diagram
 Silica Refractory
 Fireclay Refractory
 High Alumina Refractory
 Applications
 Conclusions

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 What are Refractories
ASTM C71 defines refractories as:
“Non-metallic materials having those chemical and physical
properties that made them applicable for structures, or as components
of systems, that are exposed to environments above 1000°F (811K,
538°C)”
Materials that
– Withstand high temperatures and sudden changes Examples:
 Fireclay
– Withstand action of molten slag, glass, hot gases etc.
 Silica
– Withstand load at service conditions  Mullite
– Withstand abrasive forces
– Conserve heat
– Have low coefficient of thermal expansion
 What are Refractories
 Refractory materials are used in furnaces, kilns, incinerators, and reactors.
Refractories are also used to make crucibles and moulds for casting glass and metals
and for surfacing flame deflector systems for rocket launch structures.
 Refractory materials are useful for the following functions:
 Serving as a thermal barrier between a hot medium and the wall of a containing
vessel
 Withstanding physical stresses and preventing erosion of vessel walls due to the
hot medium
 Protecting against corrosion
 Providing thermal insulation
 Refractories have multiple useful applications. In the metallurgy industry, refractories
are used for lining furnaces, kilns, reactors, and other vessels which hold and
transport hot mediums such as metal and slag. Refractories have other high
temperature applications such as fired heaters, hydrogen reformers, ammonia
primary and secondary reformers, cracking furnaces, utility boilers, catalytic cracking
units, air heaters, and sulfur furnaces.
 Refractory Industry Overview
Global Refractory Production End Use Segments

4% 5%
7%
16% 3%
4%
Rest of World Steel
China 12% Cement
37% RestOfAsia Glass
Europe Non ferrous
Others
US
26% India

74%
12%

Major Manufacturers in India

 Tata refractories Ltd.  Grindwell Norton Ltd.
 OCL India Ltd.  Indo Flow Gates Ltd.
 Orind Complete Refractory Solution  New Bharat Refractories Ltd.
 ACC Ltd.  Nataraj Ceramics
 Carborundum Universal Ltd  Pacific Refractories Ltd.

The Global Refractories Manufacturers like as Saint-Gobain (France), RHI Magnesita

(Austria), Corning Incorporated (US), Morgan Advanced Materials (UK), and Shinagawa
Refractories (Japan).
 Role of Refractories
 Refractory materials have a crucial impact on the cost and quality of steel products. The
diversification on steel products and their cleanliness requirement in recent years have
increased the demand for high quality refractory. High quality refractory at a cheaper
cost is the main requirement.

Refractories perform four basic functions

(i) They act as a thermal barrier between a hot medium (e.g., flue gases, liquid
metal, molten slags, and molten salts) and the wall of the containing vessel;
(ii) They insure a strong physical protection, preventing the erosion of walls by the
circulating hot medium;
(iii) They represent a chemical protective barrier against corrosion;
(iv) They act as thermal insulation, insuring heat retention.

Selection of Refractories: ● ceramics industry;

● foundry;
 Area of application
● aluminium production;
 Working temperatures ● precision foundry;
 Extent of abrasion and impact ● cement and lime industry;
 Heat transfer and fuel conservation ● waste incineration plants;
 Cost consideration ● industrial boilers;
● petrochemical industry;
 Role of Refractories
What are Refractories used for?
 Refractories are used by the metallurgy industry in the internal linings of furnaces,
kilns, reactors and other vessels for holding and transporting metal and slag.
 In non-metallurgical industries, the refractories are mostly installed on fired heaters,
hydrogen reformers, ammonia primary and secondary reformers, cracking furnaces,
utility boilers, catalytic cracking units, coke calciner, sulfur furnaces, air heaters, ducting,
stacks, etc.
 Majority of these listed equipment operate under high pressure, and operating
temperature can vary from very low to very high (approximately 900°F to 2900°F).
 The refractory materials are therefore needed to withstand temperatures over and
above these temperatures.
 Due to the extremely high melting point of common metals like iron, nickel and
copper, metallurgists have to raise furnace temperatures to over 2800°F.
 Properties of Refractories
A good refractory material should have the following properties:

It should be able to withstand high temperatures generated in the furnace.

It should be able to withstand sudden alternating heating and cooling, i.e., thermal
shocks.
It should be able to withstand abrasion and rough usage.
Its contraction and expansion due to the inevitable temperature variation should be
minimum possible.
It should be able to withstand fluxing action of the slags and the corrosive action of
gases.
It should have good heat insulating properties.
It should be chemically inactive at elevated temperatures.
It should be impermeable to gases and liquids as far as possible.
If used in electric furnaces, it must have low electrical conductivity.
 Classifications
Refractories can be classified on the basis of
 Chemical composition
 Method of manufacture
 Fusion temperature
Chemical composition
 Acidic Refractories (SiO2 , Fireclay)
 Basic Refractories (MgO, Dolomite)
 Neutral Refractories (Al2O3, Cr2O3) Fusion temperature
 Super Refractories (ZrO2, ThO2)  Normal refractory 1580 - 1780° (Fire clay)
Method of manufacture  High refractory 1780 - 2000° (Chromite)
 Super refractory > 2000° (Zircon)
- Dry press process
- Fused cast
Shaped
- Hand molded
- Formed (normal, fired or chemically bonded)
- Un-formed (monolithic-plastic, ramming and gunning mass, castables)
Unshaped
- Un-formed Dry Vibratable refractories.
 Classifications
Acidic refractories
 Acidic refractories are generally impervious to acidic materials but easily attacked by basic
materials, and are thus used with acidic slag in acidic environments.
 They include substances such as silica, alumina, and fire clay brick refractories. Notable
reagents that can attack both alumina and silica are hydrofluoric acid, phosphoric acid, and
fluorinated gases (e.g. HF, F2). At high temperatures, acidic refractories may also react with
limes and basic oxides.
Silica refractories are refractories containing more than 93% silicon oxide (SiO2). They are
acidic, have high resistance to thermal shock, flux and slag resistance, and high spalling
resistance. Silica bricks are often used in the iron and steel industry as furnace materials. An
important property of silica brick is its ability to maintain hardness under high loads until its
fusion point.
Zirconia refractories are refractories primarily composed of zirconium oxide (ZrO2). They are
often used for glass furnaces because they have low thermal conductivity, are not easily wetted
by molten glass and have low reactivity with molten glass. These refractories are also useful for
applications in high temperature construction materials.
Aluminosilicate refractories mainly consist of alumina (Al2O3) and silica (SiO2).
Aluminosilicate refractories can be semi acidic, fireclay composite, or high alumina content
composite.
 Classifications
Basic refractories
Basic refractories are used in areas where slags and atmosphere are basic. They are stable to
alkaline materials but can react to acids. The main raw materials belong to the RO group, of which
magnesia (MgO) is a common example. Other examples include dolomite and chrome-
magnesia. For the first half of the twentieth century, the steel making process used
artificial periclase (roasted magnesite) as a furnace lining material.
Magnesite refractories are composed of ≥ 85% magnesium oxide (MgO). They have high slag
resistance to lime and iron-rich slags, strong abrasion and corrosion resistance, and high refractoriness
under load, and are typically used in metallurgical furnaces.
Dolomite refractories mainly consist of calcium magnesium carbonate. Typically, dolomite refractories
are used in converter and refining furnaces.
Magnesia-chrome refractories mainly consist of magnesium oxide (MgO) and chromium oxide
(Cr2O3). These refractories have high refractoriness and have a high tolerance for corrosive
environments.
Neutral refractories
These are used in areas where slags and atmosphere are either acidic or basic and are chemically
stable to both acids and bases. The main raw materials belong to, but are not confined to, the
R2O3 group. Common examples of these materials are alumina (Al2O3), chromia (Cr2O3) and carbon.
Carbon graphite refractories mainly consist of carbon. These refractories are often used in highly
reducing environments, and their properties of high refractoriness allow them excellent thermal
stability and resistance to slags. Chromite refractories are composed of sintered magnesia and
chromia. They have constant volume at high temperatures, high refractoriness, and high resistance to
slags. Alumina refractories are composed of ≥ 50% alumina (Al2O3).
 Classifications
Shaped
 These have standard size and shapes. These may be further divided into standard shapes and
special shapes.
 Standard shapes have dimension that are conformed by most refractory manufacturers and are
generally applicable to kilns or furnaces of the same types. Standard shapes are usually bricks that
have a standard dimension of 9 × 41⁄2 × 21⁄2 inches (230 × 114 × 64 mm) and this dimension is
called a "one brick equivalent". "Brick equivalents" are used in estimating how many refractory
bricks it takes to make an installation into an industrial furnace. There are ranges of standard
shapes of different sizes manufactured to produce walls, roofs, arches, tubes and circular apertures
etc.
 Special shapes are specifically made for specific locations within furnaces and for particular kilns or
furnaces. Special shapes are usually less dense and therefore less hard wearing than standard
shapes.

Unshaped (monolithic refractories)

These are without definite form and are only given shape upon application. These types are better
known as monolithic refractories. The common examples are plastic masses, Ramming masses,
castables, gunning masses, fettling mix, mortars etc.
Dry vibration linings often used in Induction furnace linings are also monolithic, and sold and
transported as a dry powder, usually with a magnesia/alumina composition with additions of other
chemicals for altering specific properties. They are also finding more applications in blast furnace
linings, although this use is still rare.
 Classifications
Unshaped (monolithic refractories)
Monolithic refractories are replacing conventional brick refractories in steelmaking and
other metal extraction industries. Monolithic refractories are loose materials which can
be used to form joint free lining. The main advantages of monolithic linings are

• Grater volume stability

• Better spalling tendency
• Elimination of joint compared with brick lining
• Can be installed in hot standby mode
• Transportion is easier

Monolithic refractories can be installed by casting, spraying etc. Ramming masses are
used mostly in cold condition so that desired shapes can be obtained with accuracy.
Types of Monolithic Refractories

Castable Refractories Insulating Castables

Plastic Refractories Ramming Mixes
Patching Refractories Coating Refractories
Mortars Gunning Mixes
Fettling Mixes
 Classifications
Based on refractoriness
Refractoriness is the property of a refractory's multiphase to reach a specific softening degree at
high temperature without load, and is measured with a pyrometric cone equivalent (PCE) test.
Refractories are classified as:
 Super duty: PCE value of 33–38
 High duty: PCE value of 30–33
 Intermediate duty: PCE value of 28–30
 Low duty: PCE value of 19–28

Super heat duty refractories – These refractories have refractoriness greater than 1730 deg C
and have pyrometric cone equivalent (PCE) value greater than 33. Example of these refractories
is magnesite bricks.
High heat duty refractories – These refractories have refractoriness in the range of 1670 deg C
to 1730 deg C and have pyrometric cone equivalent (PCE) value in the range of 30 to 33.
Example of these refractories is chromite bricks.
Intermediate heat duty refractories – These refractories have refractoriness in the range of
1630 deg C to 1670 deg C and have pyrometric cone equivalent (PCE) value in the range of 28
to 30. Example of these refractories is fire clay bricks.
Low heat duty refractories – These refractories have refractoriness in the range of 1520 deg C
to 1630 deg C and have pyrometric cone equivalent (PCE) value in the range of 19 to 28.
Example of these refractories is silica bricks.
 Classifications
Based on thermal conductivity
 Refractories may be classified by thermal conductivity as either conducting, nonconducting,
or insulating.
 Examples of conducting refractories are SiC and ZrC, whereas examples of nonconducting
refractories are silica and alumina.
 Insulating refractories include calcium silicate materials, kaolin, and zirconia.
 Insulating refractories are used to reduce the rate of heat loss through furnace walls. These
refractories have low thermal conductivity due to a high degree of porosity, with a desired
porous structure of small, uniform pores evenly distributed throughout the refractory brick
in order to minimize thermal conductivity. Insulating refractories can be further classified
into four types:
 Heat-resistant insulating materials with application temperatures ≤ 1100 °C
 Refractory insulating materials with application temperatures ≤ 1400 °C
 High refractory insulating materials with application temperatures ≤ 1700 °C
 Ultra-high refractory insulating materials with application temperatures ≤ 2000 °C
 Classifications
Insulating refractories
 These are high porosity refractories having low thermal conductivity used for
reducing the rate of heat flow (heat losses) to maximize heat conservation within
the furnace.
 The development and application of a wide variety of insulating refractory
materials are gaining importance with increasing energy costs in present days. The
production of brick shape refractories utilises China clay, asbestos (kieselguhr),
glass wool, mica (vermiculite), bubble alumina, carbon, paper wool, ceramic fibers,
saw dust, etc. as raw materials.

Cermets
The refractories produced from the mixtures of high purity refractory oxides, carbides,
borides, and metals or alloys fall under this category. Depending on the composition
and quality, they are used as abrasives (cutting, grinding, boring tools), in parts of
spacecrafts, missiles, atomic power plants, etc.
 Properties of Refractories
The quality of a refractory and its suitability for a particular application primarily depends
on its physical, chemical and mineralogical properties. The most common properties that
are considered in selection the optimum refractory lining configuration are listed below

1. Refractoriness
2. Porosity and Slag permeability
3. Strength
4. Specific gravity
5. PCE (Pyrometric Cone Equivalent) value
6. RUL (Refractoriness Under Load) value
7. Creep at high temperature
8. Hot Modulus of Rupture (HMOR)
9. Corrosion Resistance
10. Abrasion, Erosion Resistance
11. Thermal shock resistance
12. Spalling Resistance
13. Permanent Linear change (PLC) on reheating
14. Thermal Conductivity
15. Apparent Porosity
16. Bulk Density
17. Cold Crushing Strength (CCS)
 Properties of Refractories
Refractoriness
Refractoriness is a property at which a refractory will deform under its own load. The
refractoriness is indicated by PCE (Pyrometric cone equivalent). It should be higher than
the application temperatures. Refractoriness decreases when refractory is under load.
Therefore more important is refractoriness under load (RUL) rather than refractoriness.

Porosity and Slag permeability

Porosity affects chemical attack by molten slag, metal and gases. Decrease in porosity
increases strength and thermal Conductivity.

Strength
It is the resistance of the refractory to compressive loads, tension and shear stresses.
In taller furnaces, the refractory has to support a heavy load; hence strength under the
combined effect of temperature and load, i.e. refractoriness under load is important.

Specific gravity
Specific gravity of the refractory is important to consider the weight of a brick. Cost of
bricks of higher specific gravity is more that of lower specific gravity. But strength of
bricks of higher specific gravity is greater than one with lower specific gravity.
 Properties of Refractories
PCE (Pyrometric Cone Equivalent) value
It is the measure of refractory’s ability to sustain high temperature without fusion or
deformation. This is measured by heating a standard size cone made of the material to
be tested in a furnace along with another standard cone having refractoriness very close
to the test material (determined by a pre-test), and noting the furnace temperature at
bending (9′ or 3′ o’clock positions viewed upside down) of the cone inclined at one end
due to its own weight.

RUL (Refractoriness Under Load) value

It is the capability of a brick to sustain itself without breaking at high temperature under
pressure of overlying load. This working load could be due to burden, liquid metal or its
own structural weight. In simple words, RUL is the crushing strength of a brick at
elevated temperature. The crushing strength of the refractory brick is lowered at
elevated temperature due to fusion/melting of grain boundaries.

Creep at high temperature

Creep is a property which indicates deformation of the refractory at high temperature
which is subjected to stress for longer period.
 Properties of Refractories
High Temperature Modulus of Rupture (HMOR)
It is the maximum stress that a rectangular test piece of defined size can withstand when
it is bent in a three point bending device. It is expressed as N/mm2 or MPa.

Corrosion Resistance
It is the wear and tear of refractories caused by static chemical attack of slag. The eating
away of refractory material due to chemical reaction between refractory and molten fluid
(slag) at high temperature is termed as ‘refractory corrosion’.

Erosion Resistance
The ability of a refractory to sustain the mechanical erosive action of sliding burden,
moving products (liquid melt and slag), flowing gases (e.g. hot flue gases laden with solid
particles) is termed as ‘erosion resistance’.

Thermal shock resistance

Thermal shock resistance is a measure of refractory property when it is exposed to
alternate heating and cooling. This thermal shock leads to breaking of refractory
particles which is termed as ‘spalling’ and loss of strength due to micro-cracks and is
noted as MOR value after thermal treatment
 Properties of Refractories
Spalling
Spalling relates to fracture of refractory brick which may occur due to the following
reasons:
• A temperature gradient in the brick which is caused by sudden heating or cooling.
• Compression in a structure of refractory due to expansion
• Variation in coefficient of thermal expansion between the surface layer and the body of
the brick
• Variation in coefficient of thermal expansion between the surface layer and the body of
the brick is due to slag penetration or due to structural change.
Thermal diffusivity is
the thermal conductivit
y divided by density and
specific heat capacity at
constant pressure. It
has the SI derived unit
of m2/s.
 Properties of Refractories
Permanent Linear change (PLC) on reheating
In materials certain permanent changes occur during heating and these changes may be
due to
• Change in the allotropic form
• Chemical reaction
• Liquid phase formative
• Sintering reactions

These changes determine the volume stability and expansion and shrinkage of the refractory at high
temperatures.

Thermal conductivity
Thermal conductivity of the bricks determines heat losses. Increase in porosity decreases thermal
conductivity but at the same time decreases strength also. It is defined as the quantity of heat that
will flow through a unit area in a direction normal to the surface area in a given time with a known
temperature gradient under steady state thermal conditions. It is indicative of heat flow
characteristics of the refractory and depends upon the nature of mineralogical constituents as well
as the physical properties of the refractories.
 Properties of Refractories
Porosity
Porosity is a measure of the vacant space as pores and voids/cavities in the refractory material. The
pores present in refractory are of three types: open pores, inter-connected pores and sealed pores.
These are explained in the following sections:
a. Open pores
These have one of their ends on the outer surface of the particle. This open end allows the
movement of fluids (gas/liquid) to the interior location of the particle permitting chemical reaction
and adsorption/absorption processes. The liquid metal may penetrate under pressure and get
solidified to cause refractory failure. The refractory with large sized open pores are undesirable for
places facing liquid metal or slag.

b. Interconnected pores
These have both of their ends opening to the outer surface of the refractory. This allows a free
movement of fluids (gas/liquid) and offers site for chemical reactions and adsorption/absorption
of fluids. Such pores are useful in manufacturing ceramic filters, but are not desirable in refractory
brick used in furnaces which may cause leakage of gases in the furnace.

c. Sealed pores
There are deep seated and do not open up to the surface of the particle. These sealed pores do not
offer any site for chemical reaction nor allow adsorption/absorption of fluids. However, these
sealed pores act as a good thermal barrier and increase the heat insulating power of the material.
Such sealed pores are useful while making heat insulating materials.
 Properties of Refractories
Density
The refractory is a porous material, and therefore its density is seriously affected by pore volume.
Following three terms are used to differentiate various types of density values:
a. True density
This refers to the ratio of mass to volume of solid particle without any pores or cavities.
b. Apparent density
It refers to the ratio of mass to volume of a single solid particle including closed pores (i.e., volume
of solid material + volume of closed pores within the particle).
c. Bulk density
It refers to the ratio of bulk mass to total bulk volume (solid volume + pore volume + void volume)
of the refractory brick.
An increase in bulk density increases the volume stability, the heat capacity, as well as the resistance
to abrasion and slag penetration.

Cold Crushing Strength (CCS)

The cold crushing strength (CCS) represents the ability of a refractory to resist failure under
compressive load at room temperature. The compressive load is applied on the refractory block till
its fracture. The CCS is then calculated as total load applied divided by the surface area.
Calculate the cold crushing strength using : S = W/A
S = cold crushing strength, lbf/in. (MPa),
W = total maximum load indicated by the testing machine, lbf (N), and
A = average of the areas of the top and bottom of the specimen perpendicular to the line of application of
the load, in2 (mm2).
Manufacturing Process
Manufacturing Process
 Aspects of Phase Diagrams in RT
 From a practical stand point, Phase diagram may be looked at as road map.
 They provide valuable information on directions to go in order to tailor-make materials of
sufficient resistance to melting for their possible use at high temperatures.
 The refractoriness of a mixture of a given composition is expressed by the liquidies-solidus
relations. Hence this diagram for common refractory components constitute the basis
equilibrium relations in refractory systems.
 In as much as a refractory should contain as little liquid as possible at the temperature of
application, the solidus rather than liquidus, be most usefulness for refractory behavior.

 A phase diagram is a graph which shows under what conditions of temperature and
pressure distinct phases of matter occur. The simplest phase diagrams are of pure
substances. These diagrams plot pressure on the y-axis and temperature on the x-axis.
 A phase is a homogeneous, physically distinct, and mechanically separable portion of matter.
Typical phases are solid, liquid and gas.
 A component is one of a collection of chemically-independent constituents of a system. The
number of components represents the minimum number of independent species necessary
to define the composition of all phases of the system.
 Degree of freedom is each of a number of independent factors required to specify a system at
equilibrium.
 The phase rule states that F = C − P + 2. Thus, for a one-component system with
one phase, the number of degrees of freedom is two, and any temperature and pressure,
within limits, can be attained.
 SiO2-Al2O3 Phase Diagram

 Silica Refractory
 Fireclay Refractory
 Sillimanite Refractory
 Mullite Refractory
 Corundum Refractory

Silica Fireclay Sillimanite Mullite Corundum

Al2O3 Content < 1% 25-45% 45-65% 65-75% > 75%
 Silica Refractory
 It contains major amount of silica (>93 wt%) with minor amount CaO, (2-3%)
Al2O3(0.5-1%) and Fe2O3 (1-1.5%).
 It is 2 types : Normal Silica (<1% Al2O3) brick & Super-duty Silica (<0.5% Al2O3) brick.

Parameters Value
Properties:
• High load capacity up to 1600oC Refractoriness 1730 oC
• High resistance to attack by Fe2O3 & alkali
•. Good thermal shock resistance above 600oC Apparent Porosity 21%
• Refractoriness around 1723oC
• Thermal conductivity is good at 1000oC Specific Gravity 2.33
• Low thermal expansion co-efficient at high temp
CCS 40 MPa
• High thermal expansion co-efficient at low temp
RUL 1620 oC

Thermal Expansion 1.22% @ 1000 oC

Uses:
• Open hearth furnace, Coke oven, Arc furnace, Glass tank furnace etc.
 Fireclay Refractory
 It contains 25 - 45% Al2O3 and 55 - 75% SiO2.
Al2O3 (%) Refractoriness
Medium duty 30 ‐ 32 1665
High duty 38 ‐ 40 1700 ‐ 1717
Super duty 42 - 45 1743 ‐ 1763

Parameters Value
Properties: Refractoriness 1760 oC
• Low thermal expansion coefficient
• Low thermal conductivity Apparent Porosity 15-17%
• Low specific gravity
• Low strength at high temperature Specific Gravity 2.15-2.25
• Less slag resistance CCS 39 MPa

RUL 1420 oC
Uses:
• Furnaces, Regenerators, Ovens, Laddle, Blust Thermal Expansion 0.5-0.6% @ 1000 oC
furnace and Kilns.
 High Al2O3 Refractory
 It contains 45-99% Al2O3. In this group the refractories are Sillimanite, Andalusite , Kyanite,
Mullite and Corundum.
 Corrosion ratio of high alumina bricks decreases with increasing alumina content but the slag
penetration increase with increasing alumina content.
Parameters Value
Properties:
• High refractoriness Refractoriness 1900 oC
• High mechanical strength
Apparent Porosity 15%
• High slag resistance
• High specific gravity Specific Gravity 3.3
• High thermal conductivity
• Low thermal expansion co-efficient CCS 88 MPa

Uses: RUL 1700 oC

• Cement, Lime and ceramic kilns, Glass tanks,
Crucibles for melting a wide range of metals Thermal Expansion 0.5% @ 1000 oC
hearth & Shaft of blast furnaces
Applications
 Conclusions

 The function of refractories

 The classification and types of refractories
 The selection aspects of right refractory material
 The characteristics and properties of few acidic refractories
 Few applications of refractories