Refractory : Introduction

Among the different classes of ceramics, refractories are the materials that can withstand high
temperature under high load. In other words, refractories are heat-resistant materials that constitute
the linings for high-temperature furnaces and reactors and other processing units. They are resistant
to thermal stress and other thermal energy related physical phenomena, also are under mechanical
loads & shocks, resist the abrasion and wear of the frictional forces and corrosion by chemical
agents. And all these phenomena occur simultaneously in an environment of the different partial
pressure of oxygen at high temperatures. Refractories act as the “backbone of industry” because they
are essentially required to support the production of all the basic and essential commodities
manufactured at high temperatures, like iron & steel, aluminium, copper, cement, glass, chemicals
& petrochemicals, ceramics, etc.

Refractories are required for withstanding the heat and any process associated with high temperature
must require refractories. The below table shows different high temperature industries and the
associated temperature of processing. All these high temperature processing industries require
refractories. Some high temperature industrial processes are shown in the below table with their
operating temperatures.

Industries Range of temperatures (oC)

Industrial drying 50 - 300
Petrochemical industries 100-1100
Hydroxide calcination 400-800
Glass annealing 400-800
Carbon combustion 400-900
Steam boiler 400-1000
Sulphide ore roasting 400-1200
Heat treatment and annealing of metals 500-1300
Aluminium and magnesium 800-1100
Carbonate calcining 800-1300
Sulphate decomposition 800-1400
Foundry industry and rolling mills 900-1400
Salt glazing of conventional ceramics 1000-1300
Fusion process 1000-2200
White ware industries 1100-1500
Glass making 1300-1500
Phosphate decompose 1300-1700
Iron making and steel making 1300-1800
Baking of carbon 1300-1800
Sintering of oxides 1300-1800
Refractories 1300-1850
Portland cement 1350-1700
Sintering of carbides 1500-1900
Sintering of carbide 1500-2000
SiC industries 1800-2200
 Refractory metals 1900-2200

Among all the different industries the consumption of refractories varies, and iron and the steel
industries consume the maximum amount refractories. The below figure shows the main refractory
consuming industries with the percentage of refractory consumption.

As, in the present day, iron and steel products are the primary most materials that human civilization
requires, the demand for iron and steel is also high compared to any other materials. Hence, the
consumption of refractories for these industries is also high, nearly three-fourth of the total refractory
manufactured. Accordingly, iron and steel industry drives the developments of the refractory
industries. The developmental activities in refractories have mostly followed the requirements
generated by the advancements in the iron and steel industries. The iron and steel industry is growing
in a big way and as a country China takes the lead role in both manufacturing and consuming of iron
and steel. Currently, the global crude steel production is about 1.6 billion t and China alone produces
close to 50%. As the refractory industries mainly follow the trend of the iron and steel industries, the
largest producer of iron and steel, China, is the largest producer and consumer of refractories;
followed by the other main iron and steel manufacturing countries. Globally total refractory
production is about 38.6 million tons. The below figure shows the primary refractory manufacturing
countries with their percentage of share to the global refractory production.
Definition

The word “Refractory” originates from Latin word “Refrāctārius”, which means stubborn
or obstinate. In Webster’s English dictionary, refractory is defined as a material that does not
significantly deform or change chemically at high temperatures. Also in other classical dictionaries,
refractories are defined as materials which are hard to work with and are especially resistant to heat
and pressure.

AS per ASTM C71 specification, refractories are defined as "non-metallic materials having those
chemical and physical properties that make them applicable for structures, or as components of
systems, that are exposed to environments above 1,000 °F (~ 811 K or 538 °C)". And as per general
understanding, refractories are non-metallic inorganic materials suitable for use at high temperatures
in furnace construction. While their primary function is to resist the high temperatures under high
load, they are also called on to resist other destructive influences during the hot processing, such as
abrasion pressure, chemical attack and rapid changes in temperature. In practical terms, refractories
are the products used for any high temperature processing to insulate the system, introduce
erosion/corrosion/abrasion resistances against the process conditions and are made mainly from non-
metallic minerals. They are designed and processed in such a way that they become resistant to the
corrosive and erosive action of hot gases, liquids and solids at high temperatures in various types of
kilns and furnaces.

While these definitions correctly identify the fundamental characteristics of refractories--their ability
to provide containment of substances at high temperature--refractories comprise a broad class of
materials having the above characteristics to varying degrees, for varying periods of time, under
varying conditions of use. There are a wide variety of refractory compositions fabricated in a large
range of shapes, sizes and forms which have been adapted to a wide variety of applications. The
common denominator is that whenever a refractory is used it will be subjected to high temperatures.
Basic property requirements

It is now clear that refractories are the industrial materials which are primarily required for any high
temperature processing and must need the two very basic features namely high temperature with-
standability (high melting point) and high strength at high temperatures. Other than these two, the
refractories need to have very low deformability against time at continuous high temperature
conditions, that is, refractories must have high creep resistances. Also, prolong use or repeated use
at high temperature may cause some dimensional changes of the refractory due to internal
adjustments, which may cause deviation from dimension accuracy and may result in failure of the
refractories. Hence very high volume stability even on prolong use is essentially required.

Again, any high temperature processing may involve some chemical reactions using various
chemicals with varying acidity and basicity, generation of liquids and gaseous products as reaction
products of the processing. Hence, the refractories have to withstand such chemical environments and
need to have excellent corrosion resistances. All the processes are involved with some input materials
and produce some desired products. Hence, refractories are associated with the flow of the materials,
both charge and product. Again these materials may be solid or liquid or gas, either in a continuous
fashion or a batch process having one entry side and one exit side (both entry of raw materials and
exit of reaction products may occur from the same side in a batch type of processing). Hence,
refractories are affected by the movement of the materials and requiring excellent resistances against
abrasion, erosion and wear.

Excellent mechanical properties, especially strength, at elevated temperatures is necessary for

refractories. Other than this, some basic thermal properties are also important. Increase in the
dimension of any materials with increasing temperature is an atomistic property (reversible thermal
expansion). Now this increasing dimension with increasing temperature may cause a problem for the
structural integrity of the refractory vessel. Different refractories with different expansion properties
change in the overall dimensions of the refractory lining and may result in a huge thermal strain and
crack. Hence, any refractory needs to have a lower thermal expansion property so that the thermal
stress generated will be minimum. Again thermal conductivity is another important fundamental
thermal property. The primary purpose of the use of a refractory is to insulate the high temperature
process from low temperature environment. Otherwise, heat will pass through resulting in an
enormous requirement of thermal energy. Hence lower thermal conductivity is preferable to reduce
the heat loss and make the process economical. Again lower thermal conductivity in a very high
temperature process may produce a very high thermal gradient in the refractory surfaces, one facing
the high temperature of the process and the other one facing the ambient atmosphere. This huge
temperature gradient will produce significant thermal strain resulting in thermal shock and cracking
of the refractory. So to have a high thermal shock resistance refractory again need to pass on heat
from the inner surface to outer one, hence, may require high thermal conductivity too.

Refractories as conventional ceramics are processed from granular / powdered materials (exactly
opposite to any metal / glass product) and the presence of porosity (void) is inherent in them. The
presence of porosity results in poor strength character and also results in weak resistances to
corrosion, abrasion, wear, etc. Hence, porosity must be minimum for a strong and dense refractory.
Similar to porosity, permeability is also detrimental to refractory. But porosity is desired for
refractories which are used only for heat insulting purposes as the pores are filled up with static air,
which is one of the best insulator and results in a high thermal efficiency of any high temperature
process.

For any application, the general requirements for a refractory material are as follows,
 It has to withstand high temperatures even under high load.
 It has to have high volume and dimensional stability
 It has to withstand sudden changes of temperatures.
 It should not deform under load on prolong time even at high temperatures
 It has to withstand the chemical actions of molten metal slag, glass, hot gases, etc.
 It has to withstand abrasive / wear / erosive forces.
 It should have a low coefficient of thermal expansion.
 It should be able to conserve heat.
 It should not contaminate the product / process material