Refractory

In materials science, a refractory (or refractory material) is a material that is resistant to

decomposition by heat or chemical attack and that retains its strength and rigidity at high
temperatures.[1] They are inorganic, non-metallic compounds that may be porous or non-porous, and
their crystallinity varies widely: they may be crystalline, polycrystalline, amorphous, or composite.
They are typically composed of oxides, carbides or nitrides of the following elements: silicon,
aluminium, magnesium, calcium, boron, chromium and zirconium.[2] Many refractories are ceramics,
but some such as graphite are not, and some ceramics such as clay pottery are not considered
refractory. Refractories are distinguished from the refractory metals, which are elemental metals and
their alloys that have high melting temperatures.

Refractory bricks in a torpedo car

used for hauling molten iron

Refractories are defined by ASTM C71 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; 538 °C)".[3] Refractory materials are used in
furnaces, kilns, incinerators, and reactors. Refractories are also used to make crucibles and molds
for casting glass and metals. The iron and steel industry and metal casting sectors use
approximately 70% of all refractories produced.[4]

Refractory materials

Refractory materials must be chemically and physically stable at high temperatures. Depending on
the operating environment, they must be resistant to thermal shock, be chemically inert, and/or have
specific ranges of thermal conductivity and of the coefficient of thermal expansion.

The oxides of aluminium (alumina), silicon (silica) and magnesium (magnesia) are the most
important materials used in the manufacturing of refractories. Another oxide usually found in
refractories is the oxide of calcium (lime).[5] Fire clays are also widely used in the manufacture of
refractories.

Refractories must be chosen according to the conditions they face. Some applications require
special refractory materials.[6] Zirconia is used when the material must withstand extremely high
temperatures.[7] Silicon carbide and carbon (graphite) are two other refractory materials used in
some very severe temperature conditions, but they cannot be used in contact with oxygen, as they
would oxidize and burn.

Binary compounds such as tungsten carbide or boron nitride can be very refractory. Hafnium
carbide is the most refractory binary compound known, with a melting point of 3890 °C.[8][9] The
ternary compound tantalum hafnium carbide has one of the highest melting points of all known
compounds (4215 °C).[10][11]

Molybdenum disilicide has a high melting point of 2030 °C and is often used as a heating element.

Uses

Refractory materials are useful for the following functions:[12][2]

1. Serving as a thermal barrier between a hot medium and the wall of a containing vessel

2. Withstanding physical stresses and preventing erosion of vessel walls due to the hot medium

3. Protecting against corrosion

4. 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 media 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.[12] They are used for surfacing flame deflectors in
rocket launch structures.[13]
Classification of refractory materials

Refractories are classified in multiple ways, based on:

1. Chemical composition

2. Method of manufacture

3. Size and shape

4. Fusion temperature

5. Refractoriness

6. Thermal conductivity

Chemical composition

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).[14] 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.[2]
Silica refractories are usually cheaper hence easily disposable. New technologies that provide
higher strength and more casting duration with less silicon oxide (90%) when mixed with organic
resins have been developed.

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 semiacidic, fireclay composite, or high alumina content composite.[15]
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, which is important e. g. when removing phosphorus from
pig iron (see Gilchrist–Thomas process). 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.[16]

Dolomite refractories mainly consist of calcium magnesium carbonate. Typically, dolomite

refractories are used in converter and refining furnaces.[17]

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.[2]

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.[18]

Alumina refractories are composed of ≥ 50% alumina (Al2O3).

Method of manufacture
1. Dry press process

2. Fused cast

3. Hand molded

4. Formed (normal, fired or chemically bonded)

 5. Un-formed (monolithic-plastic, ramming and gunning mass, castables, mortars, dry vibrating
cements.)

6. Un-formed dry refractories.

Size and shape

Refractory objects are manufactured in standard shapes and special shapes. Standard shapes have
dimensions that conform to conventions used by 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 in × 4.5 in × 2.5 in (229 mm × 114 mm × 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)

These are without prescribed form and are only given shape upon application. These types are
known as monolithic refractories. Common examples include plastic masses, ramming masses,
castables, gunning masses, fettling mix, and mortars.

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.

Fusion temperature

Refractory materials are classified into three types based on fusion temperature (melting point).

Normal refractories have a fusion temperature of 1580–1780 °C (e.g. fire clay)

High refractories have a fusion temperature of 1780–2000 °C (e.g. chromite)

Super refractories have a fusion temperature of > 2000 °C (e.g. zirconia)

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:[2]

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

Thermal conductivity

Refractories may be classified by thermal conductivity as either conducting, nonconducting, or

insulating. Examples of conducting refractories are silicon carbide (SiC) and zirconium carbide
(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:[2]

1. Heat-resistant insulating materials with application temperatures ≤ 1100 °C

2. Refractory insulating materials with application temperatures ≤ 1400 °C

3. High refractory insulating materials with application temperatures ≤ 1700 °C

4. Ultra-high refractory insulating materials with application temperatures ≤ 2000 °C

See also

Fire brick

Masonry oven

References

1. Ailsa Allaby and Michael Allaby (1996). Concise Dictionary of Earth Sciences. Oxford
Paperbacks Oxford University Press.