10/23/2017

Refractories Requirements
Kwame Nkrumah University of
Science & Technology, Kumasi, Ghana

• Withstand high temperatures and sudden changes in

temperature

MSE 351 • Withstand action of molten slag, glass, hot gases etc
• Withstand load at service conditions
Engineering Ceramics I • Withstand abrasive forces
• Conserve heat
Ing. Anthony Andrews (PhD) • Have low coefficient of thermal expansion
Department of Materials Engineering • Will not contaminate the load (material with which it
Faculty of Mechanical and Chemical Engineering comes into contact with)
College of Engineering
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Phases in contact with refractories Refractories in use

Refractory lining of a
• Slag: Mixture of acidic and basic inorganic oxides like furnace arc
SiO2, P2O5, CaO, MgO, FeO, etc.; temperature varies
from 1400℃ to 1600℃.

• Molten steel: Iron containing C, Si, Mn, P, S and

different alloying elements like Cr, Ni, Nb, Mo, W, Mo
etc.; temperature 1600℃

• Gases: CO, CO2, N2, Ar containing solid particles of Refractory walls of a

furnace interior with
Fe2O3, Fe3O4 etc.; temperature 1300℃ to 1600℃ . burner blocks
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Melting points of some pure compounds

used as refractory materials
Properties of Refractories
• Melting point
– Temperature at which a ‘test pyramid’ (cone) fails to
support its own weight

• Size/shape
– Affects stability of furnace structure
– Minimize space between construction joints

• Bulk density
– Amount of refractory material within a volume (kg/m 3)
– High bulk density => high volume stability, heat capacity
and resistance to slag penetration
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Properties of Refractories Properties of Refractories

• Porosity
– Apparent porosity is the volume of open pores as % of total • Pyrometric cones
refractory volume – Used in ceramic industries
– Low porosity => less penetration of molten material to test ‘refractoriness’ of
refractory bricks
– A large number of small pores is generally preferred to a small
number of large pores. – Each cone is mix of oxides
that melt at specific
• Cold crushing strength narrow temperature range
– Resistance of refractory to crushing (transportation) • Pyrometric Cone Equivalent (PCE)
– Indirect relevance to refractory performance • Temperature at which the refractory brick and the cone bend
• Refractory cannot be used above this temp
• Creep at high temperature
• Refractoriness under load (RUL) more important
– Deformation of refractory material under stress at given time
and temperature
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Properties of Refractories Properties of Refractories

• Volume stability, expansion & shrinkage • Thermal conductivity
– There can be permanent changes during refractory – Depends on chemical and mineralogical compositions and
silica content
service life
– Increases with rising temperature
• E.g. chemical reaction producing a new material of • High thermal conductivity desirable??
different specific gravity
– Heat transfer through brickwork required
– Occurs at high temperatures • E.g. recuperators, regenerators
• Low thermal conductivity desirable??
– Heat conservation required (insulating refractories)
• Reversible thermal expansion • E.g. heat treatment furnaces
– Phase transformations during heating and cooling – Additional insulation conserves heat but increases the hot face
temperature and hence a better quality refractory is required

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Classification of Refractory Acid Refractories

Materials
• Uses: under acidic conditions
• Based on chemical composition
– their reaction to the type of slags
• They are based on SiO2 and lie on the line between
SiO2 and Al2O3.
1. Acid refractories
2. Basic refractories • The more Al2O3 the material contains the more
3. Neutral refractories neutral the material becomes.

• Examples: fireclay, quartz, silica, aluminosilicate

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Basic Refractories Neutral Refractories

• Uses: under alkaline conditions • Uses: under either acidic or alkaline conditions

• They are based on magnesia (MgO), lime (CaO) and • They are based on chromite (Cr2O3)
Cr2O3

• Examples: Carbon, Alumina, Mullite

• High bulk density, high melting point and good
resistance to chemical attack.

• Examples: magnesite, chrome-magnesite, magnesite-

chrome, dolomite
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Special Refractories Classification of Refractory

Materials
• Silicon carbide, cermets and SiAlON are some
examples of special refractory. • Based on physical form

• They are used for special applications. 1. Shaped refractories (refractory bricks)
2. Unshaped refractories (monolithic refractories)

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Shaped Refractories Unshaped Refractories

• They have fixed shaped (e.g. bricks)
– standard shapes
– special shapes
• They are machine-pressed with high uniformity in
properties
• Special shapes are most often hand-molded and are
expected to exhibit slight variations in properties.
• They are without definite form and are only given
shape upon application.
• It forms jointless lining and are better known as
monolithic refractories.
• Types of monolithic refractories:
– Plastic refractories, castables refractories, ramming
mixes, gunning mixes, fettling mixes and motars

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Unshaped Refractories Unshaped Refractories

Castable refractories Plastic refractories
• Consists of mixtures of coarse and fine refractory grains • Mixtures prepared in stiff plastic condition
together with a bonding agent which is normally based
on high alumina cement (HAC) • Refractories delivered in blocks wrapped in
• Upon heating, binder transforms to form ceramic bond polyethylene

• Blocks sliced into pieces, rammed into place with a

rammer

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Monolithic Refractories Manufacture of Refractories

• Advantages 1. Crushing
– Elimination of joints 2. Grinding – < 200 microns
– Faster application 3. Screening – e.g. settling, magnetic separation,
– Heat savings chemical methods
– Better spalling resistance 4. Storage
– Volume stability 5. Mixing
– Easy to transport, handle, install 6. Moulding
– Reduced downtime for repairs 7. Drying
8. Firing

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Fireclay Bricks Classification of Fireclay Bricks

• Common in industry: materials available and

Other
inexpensive Brick %SiO2 %Al2O3
constituents
PCE (oC)

Super duty 49-53 40-44 5-7 1746-1760

• Consist of 25 to 45% Al2O3 and 50‐ 80% SiO2.
High duty 50-80 35-40 5-9 1690-1746
Medium duty 60-70 26-36 5-9 1635-1690
• Application areas??
Low duty 60-70 23-33 6-10 1521-1593

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High Alumina Refractories Silica Brick (Dinas)

• Al2O3 varies from 45 to 95%. • >93% SiO2 made from quality rocks
• Commonly used refractory mullite (70 – 85% Al2O3).
• High alumina => high refractoriness • Uses: Iron & steel, glass industry

• Uses: B F stoves, cement and lime rotary kilns, Advantage: no softening until fusion point is reached
electric are furnace roofs, ladle, glass making
furnaces

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Magnesite Refractories Insulating Materials

• Chemically basic: >85% magnesium oxide • Material with low heat conductivity: keeps furnace
surface temperature low.
• Made from naturally occurring magnesite (MgCO3)
• Achieved by introduction of a high degree of
porosity.
• High slag resistance, especially lime and iron
• How?

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Selecting the Right Corrosion of Refractories

Refractory
Selection criteria
• Type of furnace
• Type of metal charge
• Presence of slag
• Area of application
• Working temperatures
• Extent of abrasion and
impact
• Structural load of furnace
• Stress due to temp
gradient & fluctuations
• Chemical compatibility
• Heat transfer & fuel
conservation
• Costs
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• Refractories are used in many cases within high
temperature corrosive environment.
• Changes in the state of the environment (as “redox”
conditions or oxygen “activity”) influence the chemical
reactions
• Along with chemical reactions during corrosion,
physical changes occur that may be accelerated by the
corrosion process.
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Corrosion of Refractories
Corrosion of Refractories – is a refractory wear by loss
of thickness and mass from the exposed face of the
refractory as a consequence of chemical attack by a
corroding fluid in a process in which the refractory and
the corroding fluid react approaching chemical
equilibrium in the zone of contact between the refractory
and the fluid.
1. Phenomenological approach – chemical and physical process
2. Use of equilibrium phase diagram
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First Fundamental Principle on
Refractory and Slag Compatibility
• Complex definitions of acidity and basicity for high
temperature chemistry in steel refining
V > 1.0 implies basic slag chemistry
V < 1.0 implies acid slag chemistry
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Third Fundamental Principle on
Reactions and Temperature
Gradients
• Very steep temperature gradient => very little
penetration of slag
– corrosion reactions restricted to the slag/refractory
interface.
• Steep gradients are seen in thin-wall refractory linings
– E.g. boilers
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10/23/2017
First Fundamental Principle on
Refractory and Slag Compatibility
• “Acid” refractories tend to resist “acid” slags better than
“basic” slags
• “Basic” refractories tend to resist “basic” slags better
than “acid” slags.
• Acidity and Basicity in Solution Chemistry at RT
• Acidity and Basicity in Corrosion Chemistry at ET
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Second Fundamental Principle on
Porosity and Corrosion Rates
• Most refractories contain void space or porosity.
– Porosity may be open pores or closed pores
• No porosity => corrosion reaction limited only to the hot
face
• Porosity causes the corrosive media to penetrate the
refractory causing destructive reactions behind the hot
face.
– Implications in ceramic processing??
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Summary
• Slag corrosion by liquids occurs whenever a threshold
temperature is exceeded which is usually when melting
occurs between the refractory and the slag.
• Corrosion results in solution of refractory constituents in
the liquid phase resulting in loss of thickness of the
refractory lining.
• The rate of corrosion is dependent on the chemical
environment and on the hot face temperature of the
refractory.
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Summary
• Corrosion is primarily a chemical process, and the
potential for corrosion can be estimated by reference to
phase equilibrium diagrams.

• These diagrams can allow prediction of the “threshold

temperature” for liquid formation.

• Microscopic techniques allow identification of particular

corrosion reactions.

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