Refractories-MTEN 403

Department of Materials Science and Engineering

University of Ghana
Lecturer: Dr. Emmanuel Nyankson
Email: loyankemon@yahoo.com, enyankson@ug.edu.gh

Office Hours:
Teaching Assistant:
 Neutral Refractories
• Neutral Refractory: More compatible with neutral slag
➢High alumina

➢Carbon

➢Silicon carbide

➢Chrome
 Neutral Refractories
• High Alumina Refractory:
➢Contains between 45-99 wt.% Al2O3.
➢Composed of α-alumina and mullite
Characteristics of α-alumina are:
➢Linear thermal expansion
➢High mechanical strength
➢Higher thermal conductivity than mullite
➢Good corrosion resistance at various slags
➢High specific gravity
Mullite is the only stable compound in the Al2O3-SiO2 system under
atmospheric pressure, has low slag resistance than α-alumina and low thermal
expansion coefficient.
 Neutral Refractories
• Raw Materials for High Alumina Refractory:
➢Synthetic materials: fused alumina and mullite
➢Natural materials: bauxite, sillimanite group minerals (kyanite, andalusite and
sillimanite).
Fired and unfired bricks are the two major types of high alumina refractories.
➢High alumina bricks are used in many industries such as iron and steel, glass, cement,
lime, and incinerators.
Refer to table 1 in the lecture material for the properties of two high alumina
refractories.
Neutral Refractories
 Neutral Refractories
• Carbon:
➢The allotropic forms of carbon are:
➢Diamond
✓ Colorless and transparent
✓ Hardest material
✓ Does not conduct electricity
➢Graphite
✓ Black
✓ Conduct electricity
✓ High lubricity and is the softest of all mineral
➢Amorphous carbon: coke and charcoal
 Neutral Refractories

Soft Carbon

Graphite
Diamond

Hard Carbon
 Neutral Refractories
• Carbon refractories in the broader sense include various refractory materials,
such as

➢Coke
➢Anthracite
➢Natural graphite
Coke
➢Artificial graphite
Either baked at about 1200℃ or graphitized above 2500℃.

Anthracite
 Neutral Refractories
• Characteristics of Carbon refractories
➢Electrically conductive
➢High thermal conductivity
➢superior thermal shock resistance
➢It strength increases with temperature until graphitization starts
➢Very resistance to molten metals and slag
➢Can be easily machined
They are extensively used in hearth of blast furnace, electric arc furnaces,
crucibles, troughs for molten metals and as the lining (cathode) in Al reduction
cells.
➢Disadvantage: easily oxidized by oxygen, CO2, and steam at high temperatures.
 Neutral Refractories
• Raw materials for carbon refractories
➢Petroleum coke
➢Pitch coke
➢Metallurgical coke
➢Calcined anthracite
➢Natural graphite
➢Artificial graphite
➢ Additives such as oxides, carbides, nitrides , borides are used as needed for
improvement of properties.
 Neutral Refractories
• Petroleum coke and pitch coke: petroleum coke and pitch coke are produced
by the distillation residue of petroleum and coal tar pitch, respectively, which
are subjected to thermal decomposition around 500 ℃ to separate gas, gasoline
and liquid fractions.
• The resulting residues (green cokes) are calcined up to about 1200 ℃.
✓These cokes are used as the raw materials for artificial graphite
✓Needle coke, produced from raw oil, has low coefficient of thermal expansion and is
more graphitizable.
▪ Metallurgical coke has high mechanical strength and superior abrasion
resistance.
 Neutral Refractories
• Anthracite: has been one of the main raw materials for carbonaceous
refractories.
• Green anthracite is an organic compound containing a few percent of volatile
matter, and is an electrically insulating material.
• There are two types of anthracite
✓Gas fired anthracite: calcined at 1200 ℃.
✓Electrically calcined anthracite: calcined at a wide temperature range of 1200-2500 ℃.
The gas-fired anthracite has a high mechanical strength, but it is inferior in both
thermal shrinkage and alkali resistance.
 Neutral Refractories
▪ Natural graphite: there are two types;
✓Flake graphite: well crystalized, has particle size 0.1-2.0 mm
✓Amorphous graphite: baked to remove both moisture and volatile matter.
• Addition of flake graphite to products contributes significantly to an increase
in the thermal conductivity.
▪ Artificial graphite: can be crushed graphite from steel making electrodes
✓Pure
✓Superior in both thermal and electrical conductivity
✓Prone to molten iron and dissolves in it.
Binder: cola tar pitch which has appropriate fluidity, afford good compactness
and has high coking value, given high strength to the baked blocks is used.
 Neutral Refractories

Binder

Carbon
Calcining Crushing Mixing Forming Baking Machining Baked Carbon
aggregate
Refractory

Additives Pitch Graphitization Machining Artificial Graphite

Impregnation

Refer to Table 1 on page 147 of the lecture material for typical properties of carbon
refractories
 Neutral Refractories
• Silicon Carbide (SiC): non-oxide refractories in which SiC is the principal
constituent are called silicon carbide refractories.
• Some of the good properties of SiC are:
✓High thermal conductivity
✓Superior spalling resistance
✓Superior abrasion resistance
✓High corrosion resistance against non-oxidizing slag.
SiC is comparatively expensive.
 Neutral Refractories
• Classification:
✓High silicon carbide refractories: contains 80-90 wt.% SiC
✓Special silicon carbide refractories: > 90 wt.% SiC.
✓They can also be classified according to the sintering aid used (or bonding type).
▪ The properties of SiC varies according to the sintering aid used.
✓ silicate bonded (clay), silicon nitride bonded (Si3N4), self bonded
✓The properties of both the SiC and sintering aids influences the final properties.

Refer to Table 1 on page 151 for classification and characteristics

of SiC refractories with different bonds
 Neutral Refractories
• Example: clay-bonded SiC refractories have the following draw backs:
✓Low refractoriness
✓Softens at relatively low temperatures
✓Low resistance to thermal shock
✓Low resistance to chemical abrasion
• Example: self-bonded SiC refractories have excellent properties such as:
✓High refractoriness
✓High strength at high temperature
✓High thermal conductivity
✓Excellent thermal shock resistance
✓High corrosion resistance
 Neutral Refractories
• Properties of SiC: the general features of SiC are
✓High thermal conductivity
✓High hardness
✓Excellent wear resistance
✓Sintered high purity material has high strength at high temperature
✓Relatively low thermal expansion coefficient
✓Resistant to chemical attack by non-oxidizing slag
✓Generally superior resistance to molten metal.
The general weak points of SiC include its difficulty of sintering and use
limitation in oxidizing conditions.
 Neutral Refractories
• Raw materials
✓The SiC used in refractories is synthetic materials, that is sometimes called
“Carborundum”
✓There are several industrial methods for synthesizing SiC.
✓The Acheson method is the common method used to make refractory grade SiC.
The Acheson Method
✓High purity carbon ( pitch coke, charcoal, anthracite) and quartzite (source of SiO2)
material is placed in a furnace, around a carbon electrode.
✓Heat is generated by passing electric current through the electrode.
✓In the process, the temperature reaches 2200-2500℃, and SiC is synthesized.
𝑆𝑖𝑂2 + 3𝐶 = 𝑆𝑖𝐶 + 2𝐶𝑂
Neutral Refractories
 Neutral Refractories
Manufacturing of SiC refractory
▪ Silicate bonded SiC refractories: manufactured in the same way as
conventional refractories.
✓Clay is normally used as the sintering aid.
✓A binder is added for shaping
✓The formed pieces are fired in a non-oxidizing atmosphere, to prevent the oxidation of
the SiC.
▪ SiC refractories are also made by “reaction bonded” method.
✓Examples are silicon nitride bonding of SiC and self bonded SiC,
 Neutral Refractories
Chemical, Thermal and Mechanical Characteristics
▪ Resistance to corrosion by molten metal:
✓excellent resistance to corrosion by molten non-ferrous metals such as Al, Au, Cu and
Zn.
✓SiC must not be used for molten iron, because SiC is dissolved by molten iron.
▪ Resistance to corrosion by molten slag and molten salt:
✓High corrosion resistance to non oxidizing slag
✓High resistance to molten salt such as chloride salts
✓What do you think will happen when SiC is exposed to an oxidizing slag such as FeO?
 Neutral Refractories
Chemical, Thermal and Mechanical Characteristics
▪ Resistance to corrosion by molten metal:
✓excellent resistance to corrosion by molten non-ferrous metals such as Al, Au, Cu and
Zn.
✓SiC must not be used for molten iron, because SiC is dissolved by molten iron.
▪ Resistance to corrosion by molten slag and molten salt:
✓High corrosion resistance to non oxidizing slag
✓High resistance to molten salt such as chloride salts
✓What do you think will happen when SiC is exposed to an oxidizing slag such as FeO?

3𝐹𝑒𝑂(𝑙) + 𝑆𝑖𝐶(𝑙) = 𝑆𝑖𝑂2(𝑙) + 𝐶𝑂 + 3𝐹𝑒

 Neutral Refractories
Oxidation Characteristics-AIR
• There are two different oxidation mechanisms based on the oxygen partial
pressure.
▪ Passive Oxidation: it is the usual gas phase oxidation mechanism at relatively
high oxygen partial pressure, which results in the formation of silica.

2𝑆𝑖𝐶(𝑠) + 3𝑂2 = 2𝑆𝑖𝑂2 (𝑠 𝑜𝑟 𝑙) + 2𝐶𝑂

▪ The rate determining step of this reaction is the diffusion of oxygen through
the silica film that forms by oxidation of the surface of SiC
 Neutral Refractories
Oxidation Characteristics-AIR
▪ Active Oxidation: it occurs when the oxygen partial pressure is relatively low
and the temperature is above 1200 ℃.

𝑆𝑖𝐶(𝑠) + 𝑂2 = 𝑆𝑖𝑂(𝑔) + 𝐶𝑂
▪ The partial pressure of SiO(g) on SiC increases as the oxygen partial pressure
decreases.
✓If the oxygen partial pressure is low enough, the formation Of SiO gas is promoted and
an oxide film will not form.
✓The SiO gas diffuses out of the system and disappears.
✓The reaction rate is high when compared to that of the passive oxidation
✓Increased porosity and weakened of structure
 Neutral Refractories
Oxidation Characteristics-Humid Environment
𝑆𝑖𝐶(𝑠) + 3𝐻2 𝑂(𝑔) = 𝑆𝑖𝑂2(𝑠) + 3𝐻2(𝑔) + 𝐶𝑂(𝑔)
𝐶𝑂(𝑔) + 𝐻2 𝑂(𝑔) = 𝐶𝑂2(𝑔) + 𝐻2(𝑔)

𝑆𝑖𝐶(𝑠) + 4𝐻2 𝑂(𝑔) = 𝑆𝑖𝑂2(𝑠) + 4𝐻2(𝑔) + 𝐶𝑂2 (𝑔)

 Neutral Refractories
Reducing Environment
𝑆𝑖𝐶(𝑠) + 𝐶𝑂(𝑔) = 𝑆𝑖𝑂(𝑔) + 2𝐶(𝑔)
 Neutral Refractories
Thermal and Mechanical Properties
▪ Excellent strength at high temperature
▪ High thermal conductivity
▪ Good spalling resistance
Based on these properties, SiC refractories are used for applications where they
are exposed to repeated heating and cooling cycles.
 Neutral Refractories
Chrome Refractories:
▪ Chrome bricks are fired products composed mainly of chrome, which has high
refractoriness and good thermal shock resistance.
▪ These products are prone to collapse due to penetration and reaction with iron
oxide (a process called iron bursting)
▪ Magnesia-chrome prevents iron bursting
▪ Further improvement in corrosion resistance have been done by developing
direct-bonded magnesia-chrome bricks of high purity and high firing
temperature.
 Neutral Refractories
Raw Materials and Manufacture:
▪ The general chemical composition of natural chrome ore is FeO.Cr2O3.
✓The general oxide formula for chrome ore is represented as RO.R2O3.
✓Refer to Table 1 on page 156 for the chemical composition of chrome ore
▪ Chrome ore is sensitive to oxidation or reduction in the atmosphere at high
temperatures.
✓Expansion and shrinkage of chrome bricks.
✓Good chrome ore: high content of spinel (MgO.Al2O3), less chromite (FeO.Cr2O3) or
less FeO.
 Neutral Refractories
Chamotte Materials:
Chamotte = fired clay: Aluminosilicates
𝑥𝐴𝑙2 𝑂3 ∙ 𝑦𝑆𝑖𝑂2 ∙ 𝑧𝐻2 𝑂
Clay has a layered structure and the
building units are:
SiO4-Tetrahedra and Al2(OH)6-
Octahedra
 Neutral Refractories
What happens to clays when fired at high temperatures?
Kaolinite: 𝐴𝑙2 𝑂3 ∙ 2𝑆𝑖𝑂2 ∙ 2𝐻2 𝑂

Metakaolin
(XRD, amorphous) Spinel

RT 500 ℃ 950 ℃ 1050 ℃ 1400 ℃

Primary Mullite Secondary mullite

+ +
SiO2 (cristobalite) Cristobalite
+ +
Glass Glass
 Neutral Refractories
What happens to clays when fired at high temperatures?
Kaolinite: 𝐴𝑙2 𝑂3 ∙ 2𝑆𝑖𝑂2 ∙ 2𝐻2 𝑂

Metakaolin
(XRD, amorphous) Spinel • Secondary mullites form needles: very
necessary when there is the need for
reinforcement.
RT 500 ℃ 950 ℃ 1050 ℃ 1400 ℃ • No peaks form during the formation of
secondary mullite because the reactions are
very slow and also there is no mass loss.
Primary Mullite Secondary mullite
+ +
SiO2 (cristobalite) Cristobalite
+ +
Glass Glass
 Neutral Refractories
Critical Impurities:
K2O and Na2O are the most
critical impurities because
they reduce the
refractoriness.
 Neutral Refractories
Critical Impurities:
K2O and Na2O are the most
critical impurities because
they reduce the
refractoriness.
 Neutral Refractories
FeO also influences the
refractoriness of Al2O3-SiO2