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Refractories & Insulators

UNIT-VI

Refractories are ceramic materials that can withstand high temperatures as well as abrasive and
corrosive action of molten metals; slag’s and gases, without suffering a deformation in shape.
The main objective of a refractory is to confine heat.
On the basis of the chemical properties of their constituent substances, refractories are
classified into three categories:
i. Neutral refractories
ii. Acid refractories
iii. Basic refractories
i. Neutral refractories like graphite, zirconia and SiC refractories. These refractories are made
from weakly basic/acidic materials like carbon, zirconia (ZiO2) and chromite (FeO.CrO2)
ii. Acid refractories like alumina, silica and fire clay refractories. These refractories consist of
acidic materials like alumina (Al2O3) and silica (SiO2). These refractory materials are resistant
to acidic slag (like silica) and are often used as contaminant vessel for them. On the other hand,
they are readily attacked by basic slag’s (like CaO, MgO etc.) and contact with these oxide
materials should be avoided.
iii. Basic refractories like Magnetite and Dolomite refractories. These refractories consist of
basic materials like CaO, MgO etc. and are especially resistant to basic slags. That’s why they
find extensive use in some steel making open hearth furnaces. The presence of acidic materials
like silica is deleterious to their high-temperature performance.
Criteria of good refractory material or essential properties of good refractory materials:
The important properties are:
a. Refractoriness: is the ability of a refractory material to withstand the heat without appreciable
softening or deformation under given service conditions. The refractory material should have a
softening temperature higher than the operating temperature of the furnace in which it is to be
used.
b. Refractoriness-under-load: Temperature resistance and load bearing capacity are the two
essential qualities of a refractory. This is due to the fact that commercial refractory which are
used for lining high temperature furnace are expected to withstand varying loads of the charge.
Hence they should possess high strength and excellent temperature resistance.
c. Dimensional stability: Dimensional stability is the resistance of a material to any change in
volume when it is exposed to high temperatures, over a prolonged time.
Dimensional changes are permanent contraction and permanent expansion.
Dimensional stability is the resistance of a material to any volume changes, which may
occurs on its exposure to high temperature, over a prolonged time. These dimensional may be
permanent or reversible.
Irreversible changes may result either in the contraction or expansion of a refractory. The
permanent contraction is due to the formation of increasing amounts of liquid from the low
fusible constituent of the refractory bricks, when it is subjected to a long period of soaking at the
high temperature. The liquid gradually fills the pores of the refractory body, causing a high
degree of vitrification and shrinkage.
A typical example of such a behaviour as fireclay bricks. The shrinkage of a refractory
can also be caused by the transformation of one crystalline form of material into another more
dense form. For example, in a magnesite brick, amorphous MgO, which is relatively light (sp. gr.
3.05), is gradually converged to a more dense crystalline form, periclase (sp.gr. = 3.54). With the

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Engineering Chemistry (Refractories & Insulators)1 Prepared By B.SRINIVAS
increase in density, there is a natural shrinkage of the material. On the other hand, the
transformation of quartz (sp. Gr. = 2.65) in silica bricks to tridymite (sp. Gr. = 2.26) and
cristobalite (sp. Gr. = 2.32) at high service temperature is a accompanied by a considerable
increase in volume. This thus accounts for permanent expansion of silica bricks in service.
d. Chemical inertness: The refractory material which is used as linear for furnace walls should
be chemically inert to the chemicals charged into a furnace. It should be react with the reactants,
slags, furnace gases, fuel ashes and the products involved inside the furnace. Such reactions can
contaminate the product and gradually corrode the furnace.
e. Thermal expansion and contraction: A good refractory material should have least possible
coefficient of thermal expansion. The refractory material expands when heated and contract
when cooled. Repeated expansion and contraction contribute much towards rapid wear and tear
of the refractory structure and its rapid breakdown.
In a furnace design, allowance has to be made for thermal expansion, since practically all
solids expands, when heated and contract, when cooled. The expansion affects all dimensions of
a body. So, it is necessary that a refractory material should have least possible thermal
expansion, because;
1. Expansion of a refractory decreases the capacity of the furnace.
2. Repeated expansion and contraction contributes much towards rapid breakdown, and wear and
tear of the refractory material structure.

f. Thermal conductivity: It is one of the important properties of refractory material since it


determines the amount of heat transmission or heat loss due to radiation through it.
Refractories with low thermal conductivity are used for lining the walls of blast furnace, copper
hearth furnace etc. because they minimize the heat losses to outside radiation and help in the
maintenance of high temperatures inside the furnace.
Hence, depending upon the type of furnace, refractory materials of high or low thermal
conductivities are required by industrial operations.
In industrial operations, refractory materials of both high thermal conductivity and low
thermal conductivity are required, depending upon the type furnace. In most cases, furnace is
lined with refractories of low heat conductivities to reduce the heat losses to the outside by
radiation; otherwise maintenance of high temperatures inside the furnace will become difficult.
However, a good heat conductivity of refractory is desirable for effective heat transmission in
some furnace construction, as in muffle furnace walls, coke-oven batteries, in which charge is
separated from the flame.
The densest and least porous brick have the highest thermal conductivity, owing to the
absence of air-voids. On the other hand, in porous bricks, the entrapped air in the pores, acts as a
non-heat conducting material. For making porous refractory bricks, the refractory material is
mixed with a liberal amount of carbonaceous material, then moulded into bricks and burnt. The
carbonaceous material burns off; leaving behind minute voids, which enhances the insulating
quality.
g. Resistance to corrosion and erosion: The higher temperatures at which the furnace is
operated, viscosity of slag decreases which accelerated the chemical reaction between the slag
and refractory lining. This might lead to corrosion of refractory lining.
h. Electrical conductivity: a refractory material of low electrical conductivity is desired for
lining the walls of electrical furnace. For proper selection of refractory material it should be
always remembered that electrical conductivities of these material increases with rise in
temperature.

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Engineering Chemistry (Refractories & Insulators)2 Prepared By B.SRINIVAS
i. Porosity: Porosity of a refractory material is the ratio of its pore’s volume to the bulk volume.
Porosity can also increase the thermal shock resistance. The least porous bricks have the highest
thermal conductivity, strength, resistance to abrasion and corrosion.
All refractories contain pores, either due to manufacturing methods or deliberately by
incorporating saw-dust or cork during manufacture. The pores may be open or closed; the latter
are encountered in an oven-fired refractory. Porosity in the ratio of its pore’s volume to the bulk
volume. Thus, porosity,
P  [(W - D)/(W - A)] *100
W= Weight of saturated specimen
D= Weight of dry specimen
A = weight of saturated specimen submerged in water.

j. Thermal spalling: Rapid changes in temperature, cause uneven expansion and contraction of
refractory material, thereby leading to development of internal stresses and strains. This is in turn
are responsible for cracking, breaking or fracturing of a refractory brick or block under high
temperature, collectively known as thermal spalling. Thermal spalling can also caused by the
variation in the coefficient of expansion due to slag penetration in the refractory brick. A good
refractory must show a good resistance to thermal spalling. Spalling can be decreased by
1. Avoiding sudden temperature changes.
2. Over firing the refractories.
3. Modifying the furnace design.
4. Using high porosity, low coefficient of expansion, and good thermal conductivity refractory
bricks.
k. Permeability: It is a measure of rate of diffusion of molten solids, liquids and gases through
the connected pores of refractory. The higher the porosity is a refractory brick, the more easily it
is penetrated by gases and molten fluxes. A good refractory material should show low
permeability.
l. Texture: Texture can be coarse or fine. Coarse textured refractory bricks have good resistance
to thermal spalling, low crushing strength, and low abrasion and corrosion resistance.

Refractoriness is the ability of a refractory material to withstand the heat without appreciable
softening or deformation under given service conditions. It is generally measured as the
softening temperature. It is necessary that a refractory material should have a softening
temperature higher than the operating temperature of the furnace in which it is to be used.
Sometimes, it can be employed to withstand a temperature higher than its softening temperature
since the outer part of refractory is at a lower temperature and still in solid state, providing
strength. Thus, refractory material does not melt away although inner refractory lining in a
furnace is at a much higher temperatures than the outer ones. Most of the commercial refractories
do not exhibit sharp melting points and they soften gradually over a range of temperatures.

Measurement of refractoriness: The softening temperatures of refractories are generally


determined by seger cones also called pyrometric cones test.

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Engineering Chemistry (Refractories & Insulators)3 Prepared By B.SRINIVAS
In this test, behaviour of heat on cone of refractory and series of seger cones of standard
dimensions are compared. These cones are small pyramid shaped with triangular base, 38 mm
high with 19 mm long sides. The test refractory in the form of a cone is kept along side similar
sized standard cones and all are heated uniformly at 200C/hour or 1000C/hour or 1500C/hour or
occasionally at 6000C/hour. As seger cones are made of a particular refractory of a definite
softening temperature so they are assigned ascending seger cone numbers with increasing
softening temperature. When the test cone softens and loses its shape, one of the standard seger
cones also softens and loses its shape provided its refractoriness is close to that of the test cone.
The serial number of this standard seger cone is noted and this number is the pyrometric cone
equivalent (PCE) of the refractory under that test. When the test cone softens earlier than one
standard cone, but later than the previous one, the PCE value of the test sample is approximated
as average of the two.
The temperature at which the softening or fusion of the test-cone occurs is indicated by
its apex touching the base.

Seger-cone number Temperature (0C)


1 1110
5 1180
10 1300
15 1435
20 1530
30 1670
35 1770

.
Refractoriness-under-load: Temperature resistance and load bearing capacity are the two
essential qualities of a refractory. This is due to the fact that commercial refractories which are
used for lining high temperature furnace are expected to withstand varying loads of the charge.
Hence they should possess high strength and excellent temperature resistance.
Measurement: Seger cone test is not applicable for the measurement of strength. Because,
some refractories soften gradually over a range of temperature, but under appreciable load, they
collapse, far below their true fusion temperature. High alumina bricks and fire-clay are examples
of such refractory materials. There are some other refractory materials like silica bricks which
exert good load bearing characteristics up to their fusion temperatures as they soften over a
relatively narrow range of temperature Thus, for good results, refractoriness-under-load test is
performed by applying a load of (3.5 or 1.75 kg/cm2) to the refractory specimen (of size 5cm2
and 75cm high). The sample is then kept in carbon-resistance furnace and heating is stated at the
rate of 100C/munute. The height of the specimen is plotted vs. temperature and RUL is
expressed as the temperature at which 10% deformation takes place.

Conditional for failure of a refractory material:


i. Using a refractory material which does not have required heat, corrosion and abrasion
resistance;
ii. Using refractory material of higher thermal expansion;
iii. Using a refractory of refractoriness less than that of the operating temperature;
iv. Using basic refractory in a furnace in which acidic reactants and/or products are being
processed and vice-versa;

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Engineering Chemistry (Refractories & Insulators)4 Prepared By B.SRINIVAS
v. Using lower-duty refractory bricks in a furnace than the actual load of raw materials in
products;
vi. Using refractories which undergo considerable volume changes during their use at high
temperature.

Insulators: The substances which are capable of retarding or prohibiting the flow of heat or
electricity or sound through them are known as insulators or Insulating materials.
Insulators can be broadly classified into three categories.
Thermal Insulators
Sound Insulators
Electrical Insulators
Thermal insulators: Thermal insulators are those materials with very low thermal conductivities.
These essentially prevent heat loss. Insulation capacity is inversely proportional to conductivity.
The properties of a thermal insulator depends on
i. Pores: Most of the insulators are fibrous or granular bodies. They have pores. If the
pore size is big, then heat transfer by convection is possible. So low pore size is
preferred.
ii. Presence of moisture: Moisture enhance thermal conductivity because, water has
more thermal conductivity than air. If the pores are closed type then water can water
cannot enter. Thermal insulator should not react with water.
An ideal thermal insulator should have the following characteristics:
a. Thermal conductivity should be low
b. It should be fire proof
c. Should resist moisture absorption
d. Chemically inert
e. Low dense material
f. Should be able to bear strong load
g. Should be stable
h. Should be odorless
i. Should be inexpensive
Thermal insulators are two types:

Organic: Organic thermal insulators poses large number of small pores. These are naturally
occurring compounds.
Inorganic: Inorganic thermal insulators are asbestos, glass, calcium silicate etc.

Thermal Characteristic properties Engg. Applications.


insulators
Glass wool Soft and flexible, fire and Used as thermal insulating material in industrial
heat proof, insect proof and domestic appliances like ovens, motors and
vacuum cleaners.
Cork Possesses good porosity, Used in the lining of cold storage, bottle stoppers,
compressibility and water refrigerators.
resistance a part from good
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Engineering Chemistry (Refractories & Insulators)5 Prepared By B.SRINIVAS
thermal resistance.

Asbestos Fire and weather proof, Used as heat insulator in boilers, for roof covering
durable, light in weight. in the form of sheets.
Cellular Possess large number of Used for heat insulation in cold storage and
rubber cellular cavities. refrigerators.
Vermiculites Mica like minerals Used as heat insulators for furnace and also as
sound insulators.

Electrical insulators: The materials which are used to prevent the loss of electricity through
certain parts in an electrical system are known as electrical insulating materials or Dielectricals.
These materials apart from acting as electrical insulators can also store electric charge. Thus,
these materials have two functions, Insulation and Storage of charge.
Characteristics:
1. A good insulator possesses low electrical conductivity or high resistivity. Typical
values being 109 to 1020 ohm-cm at room temperature.
2. Dialectics used in capacitor should have high dielectric constant so that grater
amount of energy can be stored in relatively thin insulation.
3. In an insulating material dielectric loss are caused by a. the absorption of
electrical energy and leakage of current through the material.
This due to the fact that the absorption of electrical energy, under an alternating
field gives rise to dissipation of the electrical energy in the insulating material.
The leakage of current through the insulating material takes place as a result of
conduction, especially at higher temperature.
4. Good dielectric materials should have low porosity. this is due to the fact that
higher porosity increases the moisture holding capacity and moisture adversely
affects the electrical properties.
5. An ideal insulator should have least thermal expansion and contraction.
6. Good insulating materials should be chemically inert to acids, alkalies, oils,
solvents, moisture, gas fumes etc.
Important electrical insulating materials and their engineering applications:

Insulator Engg. Applications.


Air It provides insulation between the overhead transmission lines.
Nitrogen It is used in transformers to replace the harmful oxidising
atmosphere. under high pressure, it is also used as dielectric in
certain electrical capacitors.
Electronegative gases SF6 is used in electrical devices like capacitors, cables.
like SF6 & CCl4
Mineral oils In transformers, a light fraction oil like transil oil is used to allow
converting cooling. under pressure, light oils are also used in oil
filled high voltage cables. more viscous or talky oils are used to
impregnate the paper in solid type of cable.
Silicone fluids Used as coolants in radio, pulse and aircraft transformers.
Fluorinated liquids Used in transformers and small electric and radio devices.
Drying oils Used in transformers and motor coils.
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Non drying oils Used in insulating resin compositions
Paper & press boards Used for winding, cable coil insulation, primary dielectrics in
capacitors, windings and mica insulations, slot insulations of
electrical machines etc.
Inorganic fibrous Below red heat it is used in woven cloth tape, paper and wire
insulators (asbestos) covering.
Insulating varnishes Used for impregnation coatings and adhesion impregnation of
fibrous materials for improving the mechanical strength, and
decreasing the hygroscopic of the fibrous material by replacing air
in their pores.
Synthetic rubbers Silicsone rubbers used in ship wiring, aircraft cables, high
temperature arcs, motor winding insulations.

Synthetic resins PVC used in flexible wire coverings, cable sheathings, insulating
electric wires and low voltage cables.
Teflon used as capacitor dielectrics and insulating material for
almost all kinds of windings.
Rigid insulators(Glass) Used for wire coverings, line insulations, glass to metal seals and
other electrical engineering applications.

Silica Bricks:
Preparation: The raw material used for the manufacture of silica bricks are quartz, quartzite,
sand, sandstone, ganister etc. siliceous rock is first crushed and ground with 2% lime & water.
The resultant thick paste is then made into bricks by machine pressing. After drying, bricks are
burnt in kilns. In about 24 hours, the temperature is slowly raised to about 15000C. This high
temperature is maintained for about 12 hours. This step is essential since it allows quartzite to be
converted into cristobalite careful cooling is then done and it takes about 1 to 2 weeks.
Cristobalite is slowly changed into tridymite during cooling and in the final brick, the mixture of
two results.
Properties:
a. Silica bricks are yellowish in colour with speaks throughout the body.
b. These bricks are acidic and are therefore suitable for acidic furnace charges.
c. Silica bricks are remarkable for their load bearing capacity. They can withstand a load of
about 3.5 kg/cm2 up to about 16000C.
d. Silica bricks are not susceptible to thermal spalling at temperature below 8000C.
e. These bricks are light and possess high rigidity and mechanical strength.
f. These bricks do not contract in use.
Applications: Silica bricks are used in lining roof arches of open hearth furnaces and
reverberatory furnaces, gas retort and walls of coke ovens.

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Engineering Chemistry (Refractories & Insulators)7 Prepared By B.SRINIVAS