Module 7 - Ceramics, Structures and properties of ceramics
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About This Presentation
Ceramics
Slide Content
E N G G 4 1 2 :
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 1
Ceramics
Intended Learning Outcomes
After studying this chapter, you should be able to do the following:
1. Differentiate the types of ceramic materials.
2. Determine the different application and properties of the ceramics
3. Explain the processes involved in processing and fabrication of ceramic materials.
This chapter will discuss structures and properties of ceramics, as well as its applications
and processing. A ceramic is an inorganic non-metallic solid made up of either metal or non-metal
compounds that have been shaped and then hardened by heating to high temperature. In general,
they are hard, corrosion-resistant, and brittle. Ceramics are all around us. This category of
materials includes things like tiles, bricks, plates, glass, and toilets. Depending on their method of
formation, ceramics can be dense or lightweight. Typically, they will demonstrate excellent
strength and hardness properties, however, they are often brittle in nature. Ceramics can also be
formed to serve as electrically conductive materials, objects allowing electricity to pass through
their mass, or insulators, materials preventing the flow of electricity.
What are Ceramics?
A ceramic is an inorganic non-metallic solid made up of either metal or non-metal compounds
that have been shaped and then hardened by heating to high temperatures. In general, they are hard,
corrosion-resistant and brittle.
The term ceramic comes from the Greek word keramikos, which means “burnt stuff,” indicating
that desirable properties of these materials are normally achieved through a high-temperature heat
treatment process called firing.
The clay-based domestic wares, art objects and building products are familiar to us all, but
pottery is just one part of the ceramic world. Nowadays the term ‘ceramic’ has a more expansive
meaning and includes materials like glass, advanced ceramics and some cement systems as well.
STRUCTURES AND PROPERTIES OF CERAMICS
Ceramic Bonding
In an ionic bond, one of the atoms (the metal) transfers electrons to the other atom
(the nonmetal), thus becoming positively charged (cation), whereas the nonmetal becomes
Chapter
7
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 1
Ceramics
Intended Learning Outcomes
After studying this chapter, you should be able to do the following:
1. Differentiate the types of ceramic materials.
2. Determine the different application and properties of the ceramics
3. Explain the processes involved in processing and fabrication of ceramic materials.
This chapter will discuss structures and properties of ceramics, as well as its applications
and processing. A ceramic is an inorganic non-metallic solid made up of either metal or non-metal
compounds that have been shaped and then hardened by heating to high temperature. In general,
they are hard, corrosion-resistant, and brittle. Ceramics are all around us. This category of
materials includes things like tiles, bricks, plates, glass, and toilets. Depending on their method of
formation, ceramics can be dense or lightweight. Typically, they will demonstrate excellent
strength and hardness properties, however, they are often brittle in nature. Ceramics can also be
formed to serve as electrically conductive materials, objects allowing electricity to pass through
their mass, or insulators, materials preventing the flow of electricity.
What are Ceramics?
A ceramic is an inorganic non-metallic solid made up of either metal or non-metal compounds
that have been shaped and then hardened by heating to high temperatures. In general, they are hard,
corrosion-resistant and brittle.
The term ceramic comes from the Greek word keramikos, which means “burnt stuff,” indicating
that desirable properties of these materials are normally achieved through a high-temperature heat
treatment process called firing.
The clay-based domestic wares, art objects and building products are familiar to us all, but
pottery is just one part of the ceramic world. Nowadays the term ‘ceramic’ has a more expansive
meaning and includes materials like glass, advanced ceramics and some cement systems as well.
STRUCTURES AND PROPERTIES OF CERAMICS
Ceramic Bonding
In an ionic bond, one of the atoms (the metal) transfers electrons to the other atom
(the nonmetal), thus becoming positively charged (cation), whereas the nonmetal becomes
Chapter
7
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Module No. 7 – Ceramics 2
negatively charged (anion). The two ions having opposite charges attract each other with a strong
electrostatic force.
Covalent bonding instead occurs between two nonmetals, in other words two atoms that
have similar electronegativity, and involves the sharing of electron pairs between the two atoms.
Although both types of bonds occur between atoms in ceramic materials, in most of them (particularly
the oxides) the ionic bond is predominant.
The ionic and covalent bonds of ceramics are responsible for many unique properties of
these materials, such as high hardness, high melting points, low thermal expansion, and good chemical
resistance, but also for some undesirable characteristics, foremost being brittleness, which leads to
fractures unless the material is toughened by reinforcing agents or by other means.
Ceramic Crystal Structure
AX-Type Crystal Structures
Some of the common ceramic materials are those in which there are equal numbers of
cations and anions. These are often referred to as AX compounds, where A denotes the cation
and X the anion. There are several different crystal structures for AX compounds; each is typically
named after a common material that assumes the particular structure.
Rock Salt Structure
Perhaps the most common AX crystal structure is the sodium chloride (NaCl), or rock salt,
type. The coordination number for both cations and anions is 6, and therefore the cation–anion
radius ratio is between approximately 0.414 and 0.732. A unit cell for this crystal structure is
generated from an FCC arrangement of anions with one cation situated at the cube center and
one at the center of each of the 12 cube edges. An equivalent crystal structure results from a
face-centered arrangement of cations. Thus, the rock salt crystal structure may be thought of as
two interpenetrating FCC lattices—one composed of the cations, the other of anions. Some
common ceramic materials that form with this crystal structure are NaCl, MgO, MnS, LiF, and
FeO.
Figure 1. A unit cell for the rock salt or sodium chloride (NaCl) crystal structure
Adapted from Fig. 12.2, Callister 9e
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 2
negatively charged (anion). The two ions having opposite charges attract each other with a strong
electrostatic force.
Covalent bonding instead occurs between two nonmetals, in other words two atoms that
have similar electronegativity, and involves the sharing of electron pairs between the two atoms.
Although both types of bonds occur between atoms in ceramic materials, in most of them (particularly
the oxides) the ionic bond is predominant.
The ionic and covalent bonds of ceramics are responsible for many unique properties of
these materials, such as high hardness, high melting points, low thermal expansion, and good chemical
resistance, but also for some undesirable characteristics, foremost being brittleness, which leads to
fractures unless the material is toughened by reinforcing agents or by other means.
Ceramic Crystal Structure
AX-Type Crystal Structures
Some of the common ceramic materials are those in which there are equal numbers of
cations and anions. These are often referred to as AX compounds, where A denotes the cation
and X the anion. There are several different crystal structures for AX compounds; each is typically
named after a common material that assumes the particular structure.
Rock Salt Structure
Perhaps the most common AX crystal structure is the sodium chloride (NaCl), or rock salt,
type. The coordination number for both cations and anions is 6, and therefore the cation–anion
radius ratio is between approximately 0.414 and 0.732. A unit cell for this crystal structure is
generated from an FCC arrangement of anions with one cation situated at the cube center and
one at the center of each of the 12 cube edges. An equivalent crystal structure results from a
face-centered arrangement of cations. Thus, the rock salt crystal structure may be thought of as
two interpenetrating FCC lattices—one composed of the cations, the other of anions. Some
common ceramic materials that form with this crystal structure are NaCl, MgO, MnS, LiF, and
FeO.
Figure 1. A unit cell for the rock salt or sodium chloride (NaCl) crystal structure
Adapted from Fig. 12.2, Callister 9e
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Module No. 7 – Ceramics 3
Cesium Chloride Structure
Figure 2 shows a unit cell for the cesium chloride (CsCl) crystal structure; the coordination
number is 8 for both ion types. The anions are located at each of the corners of a cube, whereas
the cube center is a single cation. Interchange of anions with cations, and vice versa, produces
the same crystal structure. This is not a BCC crystal structure because ions of two different kinds
are involved.
Figure 2. A unit cellfor the Cesium Chloride (CsCl) crystal structure
Adapted from Fig. 12.3, Callister 9e
Zinc Blende Structure
A third AX structure is one in which the coordination number is 4—that is, all ions are
tetrahedrally coordinated. This is called the zinc blende, or sphalerite, structure, after the
mineralogical term for zinc sulfide (ZnS). A unit cell is presented in Figure 3, all corner and face
positions of the cubic cell are occupied by S atoms, whereas the Zn atoms fill interior tetrahedral
positions. An equivalent structure results if Zn and S atom positions are reversed. Thus, each Zn
atom is bonded to four S atoms, and vice versa. Most often the atomic bonding is highly covalent
in compounds exhibiting this crystal structure, which include ZnS, ZnTe, and SiC.
Figure 3. A unit cell for zinc blende (ZnS) crystal structure
Adapted from Fig. 12.4, Callister 9e
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 3
Cesium Chloride Structure
Figure 2 shows a unit cell for the cesium chloride (CsCl) crystal structure; the coordination
number is 8 for both ion types. The anions are located at each of the corners of a cube, whereas
the cube center is a single cation. Interchange of anions with cations, and vice versa, produces
the same crystal structure. This is not a BCC crystal structure because ions of two different kinds
are involved.
Figure 2. A unit cellfor the Cesium Chloride (CsCl) crystal structure
Adapted from Fig. 12.3, Callister 9e
Zinc Blende Structure
A third AX structure is one in which the coordination number is 4—that is, all ions are
tetrahedrally coordinated. This is called the zinc blende, or sphalerite, structure, after the
mineralogical term for zinc sulfide (ZnS). A unit cell is presented in Figure 3, all corner and face
positions of the cubic cell are occupied by S atoms, whereas the Zn atoms fill interior tetrahedral
positions. An equivalent structure results if Zn and S atom positions are reversed. Thus, each Zn
atom is bonded to four S atoms, and vice versa. Most often the atomic bonding is highly covalent
in compounds exhibiting this crystal structure, which include ZnS, ZnTe, and SiC.
Figure 3. A unit cell for zinc blende (ZnS) crystal structure
Adapted from Fig. 12.4, Callister 9e
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Module No. 7 – Ceramics 4
AmXp-Type Crystal Structures
If the charges on the cations and anions are not the same, a compound can exist with the
chemical formula AmXp, where m and/or p≠1. An example is AX2, for which a common crystal
structure is found in fluorite (CaF2). Calcium ions are positioned at the centers of cubes, with
fluorine ions at the corners. The chemical formula shows that there are only half as many Ca2
ions as F ions, and therefore the crystal structure is similar to CsCl, except that only half the center
cube positions are occupied by Ca2 ions. One unit cell consists of eight cubes, as indicated in
Figure 4. Other compounds with this crystal structure include ZrO2 (cubic), UO2, PuO2, and ThO2.
Figure 4. A unit cell for the fluorite (CaF2) crystal structures
Adapted from Fig. 12.5, Callister 9e
AmBnXp-Type Crystal Structures
It is also possible for ceramic compounds to have more than one type of cation; for two
types of cations (represented by A and B), their chemical formula may be designated as AmBnXp.
Barium titanate (BaTiO3), having both Ba2 and Ti4 cations, falls into this classification. This
material has a perovskite crystal structure and rather interesting electromechanical properties to
be discussed later. At temperatures above 120
0
C (248
0
F), the crystal structure is cubic. A unit
cell of this structure is shown in the figure below.
Figure 5. A unit cell for the perovskite crystal structure.
Adapted from Fig. 12.6, Callister 9e
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 4
AmXp-Type Crystal Structures
If the charges on the cations and anions are not the same, a compound can exist with the
chemical formula AmXp, where m and/or p≠1. An example is AX2, for which a common crystal
structure is found in fluorite (CaF2). Calcium ions are positioned at the centers of cubes, with
fluorine ions at the corners. The chemical formula shows that there are only half as many Ca2
ions as F ions, and therefore the crystal structure is similar to CsCl, except that only half the center
cube positions are occupied by Ca2 ions. One unit cell consists of eight cubes, as indicated in
Figure 4. Other compounds with this crystal structure include ZrO2 (cubic), UO2, PuO2, and ThO2.
Figure 4. A unit cell for the fluorite (CaF2) crystal structures
Adapted from Fig. 12.5, Callister 9e
AmBnXp-Type Crystal Structures
It is also possible for ceramic compounds to have more than one type of cation; for two
types of cations (represented by A and B), their chemical formula may be designated as AmBnXp.
Barium titanate (BaTiO3), having both Ba2 and Ti4 cations, falls into this classification. This
material has a perovskite crystal structure and rather interesting electromechanical properties to
be discussed later. At temperatures above 120
0
C (248
0
F), the crystal structure is cubic. A unit
cell of this structure is shown in the figure below.
Figure 5. A unit cell for the perovskite crystal structure.
Adapted from Fig. 12.6, Callister 9e
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Module No. 7 – Ceramics 5
Table 1.0 summarizes the rock salt, cesium chloride, zinc blende, fluorite, and perovskite
crystal structures in terms of cation–anion ratios and coordination numbers and gives examples
for each. Of course, many other ceramic crystal structures are possible.
Table 1.0 Summary of Some Common Ceramic Crystal Structure
Mechanical Properties of Ceramics
The properties of ceramics, however, also depend on their microstructure. Ceramics are
by definition natural or synthetic inorganic, non-metallic, polycrystalline materials. Sometimes,
even monocrystalline materials, such as diamond and sapphire, are erroneously included under
the term ceramics. Polycrystalline materials are formed by multiple crystal grains joined together
during the production process, whereas monocrystalline materials are grown as one three-
dimensional crystal. Fabrication processes of polycrystalline materials are relatively inexpensive,
when compared to single crystals. Due to these differences (e.g., multiple crystals with various
orientations, presence of grain boundaries, fabrication processes), polycrystalline materials
should really not be confused with single crystals and should be the only ones included under the
definition of ceramics. The properties and the processing of ceramics are largely affected by their
grain sizes and shapes, and characteristics such as density, hardness, mechanical strength, and
optical properties strongly correlate with the microstructure of the sintered piece.
Typical Properties of Ceramics
• High hardness
• High elastic modulus
• Low ductility
• High dimensional stability
• Good wear resistance
• High resistance to corrosion
• High weather resistance
• High melting point
• High working temperature
• Low thermal expansion
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 5
Table 1.0 summarizes the rock salt, cesium chloride, zinc blende, fluorite, and perovskite
crystal structures in terms of cation–anion ratios and coordination numbers and gives examples
for each. Of course, many other ceramic crystal structures are possible.
Table 1.0 Summary of Some Common Ceramic Crystal Structure
Mechanical Properties of Ceramics
The properties of ceramics, however, also depend on their microstructure. Ceramics are
by definition natural or synthetic inorganic, non-metallic, polycrystalline materials. Sometimes,
even monocrystalline materials, such as diamond and sapphire, are erroneously included under
the term ceramics. Polycrystalline materials are formed by multiple crystal grains joined together
during the production process, whereas monocrystalline materials are grown as one three-
dimensional crystal. Fabrication processes of polycrystalline materials are relatively inexpensive,
when compared to single crystals. Due to these differences (e.g., multiple crystals with various
orientations, presence of grain boundaries, fabrication processes), polycrystalline materials
should really not be confused with single crystals and should be the only ones included under the
definition of ceramics. The properties and the processing of ceramics are largely affected by their
grain sizes and shapes, and characteristics such as density, hardness, mechanical strength, and
optical properties strongly correlate with the microstructure of the sintered piece.
Typical Properties of Ceramics
• High hardness
• High elastic modulus
• Low ductility
• High dimensional stability
• Good wear resistance
• High resistance to corrosion
• High weather resistance
• High melting point
• High working temperature
• Low thermal expansion
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• Low to medium thermal conductivity
• Good electrical insulation
• Low to medium tensile strength
• High compressive strength
Classification of Ceramics
It is used in completely different kinds of applications and, in this regard, tend to
complement each other and also the polymers. Most ceramic materials fall into an application–
classification scheme that includes the following groups: glasses, structural clay products, white
wares, refractories, abrasives, cements, ceramic biomaterials, carbons, and the newly developed
advanced ceramics.
Figure 6. Classification of ceramic materials on the basis of application.
Adapted from Fig. 13.1, Callister 9e
Glass
The glasses are a familiar group of ceramics; containers, lenses, and fiberglass represent
typical applications. As already mentioned, they are noncrystalline silicates containing other
oxides, notably CaO, Na2O, K2O, and Al2O3, which influence the glass properties. A typical soda-
lime glass consists of approximately 70 wt% SiO2, the balance being mainly Na2O (soda) and
CaO (lime). Possibly the two prime assets of these materials are their optical transparency and
the relative ease with which they may be fabricated.
Glass-ceramic
Most inorganic glasses can be made to transform from a non-crystalline state into one that
is crystalline by the proper high-temperature heat treatment. This process is called crystallization,
and the product is a fine-grained polycrystalline material that is often called a glass-ceramic.
Glass-ceramic materials have been designed to have the following characteristics:
relatively high mechanical strengths; low coefficients of thermal expansion (to avoid thermal
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Module No. 7 – Ceramics 6
• Low to medium thermal conductivity
• Good electrical insulation
• Low to medium tensile strength
• High compressive strength
Classification of Ceramics
It is used in completely different kinds of applications and, in this regard, tend to
complement each other and also the polymers. Most ceramic materials fall into an application–
classification scheme that includes the following groups: glasses, structural clay products, white
wares, refractories, abrasives, cements, ceramic biomaterials, carbons, and the newly developed
advanced ceramics.
Figure 6. Classification of ceramic materials on the basis of application.
Adapted from Fig. 13.1, Callister 9e
Glass
The glasses are a familiar group of ceramics; containers, lenses, and fiberglass represent
typical applications. As already mentioned, they are noncrystalline silicates containing other
oxides, notably CaO, Na2O, K2O, and Al2O3, which influence the glass properties. A typical soda-
lime glass consists of approximately 70 wt% SiO2, the balance being mainly Na2O (soda) and
CaO (lime). Possibly the two prime assets of these materials are their optical transparency and
the relative ease with which they may be fabricated.
Glass-ceramic
Most inorganic glasses can be made to transform from a non-crystalline state into one that
is crystalline by the proper high-temperature heat treatment. This process is called crystallization,
and the product is a fine-grained polycrystalline material that is often called a glass-ceramic.
Glass-ceramic materials have been designed to have the following characteristics:
relatively high mechanical strengths; low coefficients of thermal expansion (to avoid thermal
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Module No. 7 – Ceramics 7
shock); good high-temperature capabilities; good dielectric properties (for electronic packaging
applications); and good biological compatibility. Some glass- ceramics may be made optically
transparent; others are opaque. Possibly the most attractive attribute of this class of materials is
the ease with which they may be fabricated; conventional glass-forming techniques may be used
conveniently in the mass production of nearly pore-free ware.
Glass–ceramics are manufactured commercially under the trade names of Pyroceram,
CorningWare, Cercor, and Vision. The most common uses for these materials are as ovenware,
tableware, oven windows, and range tops—primarily because of their strength and excellent
resistance to thermal shock. They also serve as electrical insulators and as substrates for printed
circuit boards and are used for architectural cladding and for heat exchangers and regenerators.
Table 2. Composition and Characteristics of Some Common Commercial Glasses
Adapted from Table 13.1, Callister 9e
CLAY PRODUCTS
One of the most widely used ceramic raw materials is clay. This inexpensive ingredient,
found naturally in great abundance, often is used as mined without any upgrading of quality.
Another reason for its popularity lies in the ease with which clay products may be formed; when
mixed in the proper proportions, clay and water form a plastic mass that is very amenable to
shaping. The formed piece is dried to remove some of the moisture, after which it is fired at an
elevated temperature to improve its mechanical strength. Most clay-based products fall within two
broad classifications: the structural clay products and whitewares. Structural clay products include
building bricks, tiles, and sewer pipes—applications in which structural integrity is important.
Whiteware ceramics become white after high-temperature firing. Included in this group are
porcelain, pottery, tableware, china, and plumbing fixtures (sanitary ware). In addition to clay,
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 7
shock); good high-temperature capabilities; good dielectric properties (for electronic packaging
applications); and good biological compatibility. Some glass- ceramics may be made optically
transparent; others are opaque. Possibly the most attractive attribute of this class of materials is
the ease with which they may be fabricated; conventional glass-forming techniques may be used
conveniently in the mass production of nearly pore-free ware.
Glass–ceramics are manufactured commercially under the trade names of Pyroceram,
CorningWare, Cercor, and Vision. The most common uses for these materials are as ovenware,
tableware, oven windows, and range tops—primarily because of their strength and excellent
resistance to thermal shock. They also serve as electrical insulators and as substrates for printed
circuit boards and are used for architectural cladding and for heat exchangers and regenerators.
Table 2. Composition and Characteristics of Some Common Commercial Glasses
Adapted from Table 13.1, Callister 9e
CLAY PRODUCTS
One of the most widely used ceramic raw materials is clay. This inexpensive ingredient,
found naturally in great abundance, often is used as mined without any upgrading of quality.
Another reason for its popularity lies in the ease with which clay products may be formed; when
mixed in the proper proportions, clay and water form a plastic mass that is very amenable to
shaping. The formed piece is dried to remove some of the moisture, after which it is fired at an
elevated temperature to improve its mechanical strength. Most clay-based products fall within two
broad classifications: the structural clay products and whitewares. Structural clay products include
building bricks, tiles, and sewer pipes—applications in which structural integrity is important.
Whiteware ceramics become white after high-temperature firing. Included in this group are
porcelain, pottery, tableware, china, and plumbing fixtures (sanitary ware). In addition to clay,
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Module No. 7 – Ceramics 8
many of these products also contain nonplastic ingredients, which influence the changes that take
place during the drying and firing processes and the characteristics of the finished piece
REFRACTORIES
Another important class of ceramics that are used in large tonnages is the refractory
ceramics. The salient properties of these materials include the capacity to withstand high
temperatures without melting or decomposing and the capacity to remain unreactive and inert
when exposed to severe environments. In addition, the ability to provide thermal insulation is often
an important consideration. Refractory materials are marketed in a variety of forms, but bricks are
the most common. Typical applications include furnace linings for metal refining, glass
manufacturing, metallurgical heat treatment, and power generation.
On this basis, there are several classifications—fireclay, silica, basic, and special
refractories. Compositions for a number of commercial refractories are listed in Table 13.2. For
many commercial materials, the raw ingredients consist of both large (or grog) particles and fine
particles, which may have different compositions. Upon firing, the fine particles normally are
involved in the formation of a bonding phase, which is responsible for the increased strength of
the brick; this phase may be predominantly either glassy or crystalline. The service temperature
is normally below that at which the refractory piece was fired.
Table 3. Composition of Five Common Ceramic Refractory Materials
Adapted from Table 13.2, Callister 9e
Fireclay Refractories
Fireclay bricks are used principally in furnace construction to confine hot atmospheres and
to thermally insulate structural members from excessive temperatures. For fireclay brick, strength
is not ordinarily an important consideration because support of structural loads is usually not
required. Some control is normally maintained over the dimensional accuracy and stability of the
finished product.
Silica Refractories
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many of these products also contain nonplastic ingredients, which influence the changes that take
place during the drying and firing processes and the characteristics of the finished piece
REFRACTORIES
Another important class of ceramics that are used in large tonnages is the refractory
ceramics. The salient properties of these materials include the capacity to withstand high
temperatures without melting or decomposing and the capacity to remain unreactive and inert
when exposed to severe environments. In addition, the ability to provide thermal insulation is often
an important consideration. Refractory materials are marketed in a variety of forms, but bricks are
the most common. Typical applications include furnace linings for metal refining, glass
manufacturing, metallurgical heat treatment, and power generation.
On this basis, there are several classifications—fireclay, silica, basic, and special
refractories. Compositions for a number of commercial refractories are listed in Table 13.2. For
many commercial materials, the raw ingredients consist of both large (or grog) particles and fine
particles, which may have different compositions. Upon firing, the fine particles normally are
involved in the formation of a bonding phase, which is responsible for the increased strength of
the brick; this phase may be predominantly either glassy or crystalline. The service temperature
is normally below that at which the refractory piece was fired.
Table 3. Composition of Five Common Ceramic Refractory Materials
Adapted from Table 13.2, Callister 9e
Fireclay Refractories
Fireclay bricks are used principally in furnace construction to confine hot atmospheres and
to thermally insulate structural members from excessive temperatures. For fireclay brick, strength
is not ordinarily an important consideration because support of structural loads is usually not
required. Some control is normally maintained over the dimensional accuracy and stability of the
finished product.
Silica Refractories
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The prime ingredient for silica refractories, sometimes termed acid refractories, is silica.
These materials, well known for their high-temperature load-bearing capacity, are commonly used
in the arched roofs of steel- and glass-making furnaces; for these applications, temperatures as
high as 1650
0
C (3000
0
F) may be realized. Under these conditions, some small portion of the
brick actually exists as a liquid. The presence of even small concentrations of alumina has an
adverse influence on the performance of these refractories.
These refractory materials are also resistant to slags that are rich in silica (called acid
slags) and are often used as containment vessels for them. However, they are readily attacked
by slags composed of a high proportion of CaO and/or MgO (basic slags), and contact with these
oxide materials should be avoided.
Basic Refractories
The refractories that are rich in periclase, or magnesia (MgO), are termed basic; they may
also contain calcium, chromium, and iron compounds. The presence of silica is deleterious to
their high-temperature performance. Basic refractories are especially resistant to attack by slags
containing high concentrations of MgO and CaO and find extensive use in some steel-making
open hearth furnaces.
Special Refractories
Yet other ceramic materials are used for rather specialized refractory applications. Some
of these are relatively high-purity oxide materials, many of which may be produced with very little
porosity. Included in this group are alumina, silica, magnesia, beryllia (BeO), zirconia (ZrO2), and
mullite (3Al2O3–2SiO2). Others include carbide compounds, in addition to carbon and graphite.
Silicon carbide (SiC) has been used for electrical resistance heating elements, as a crucible
material, and in internal furnace components. Carbon and graphite are very refractory, but find
limited application because they are susceptible to oxidation at temperatures in excess of about
800C (1470F). As would be expected, these specialized refractories are relatively expensive.
ABRASIVES
Abrasive ceramics are used to wear, grind, or cut away other material, which necessarily
is softer. Therefore, the prime requisite for this group of materials is hardness or wear resistance;
in addition, a high degree of toughness is essential to ensure that the abrasive particles do not
easily fracture. Furthermore, high temperatures may be produced from abrasive frictional forces,
so some refractoriness is also desirable. Diamonds, both natural and synthetic, are used as
abrasives; however, they are relatively expensive. The more common ceramic abrasives include
silicon carbide, tungsten carbide (WC), aluminum oxide (or corundum), and silica sand.
Coated abrasives are those in which an abrasive powder is coated on some type of paper
or cloth material; sandpaper is probably the most familiar example. Wood, metals, ceramics, and
plastics are all frequently ground and polished using this form of abrasive. Grinding, lapping, and
polishing wheels often employ loose abrasive grains that are delivered in some type of oil- or
water-based vehicle. Diamonds, corundum, silicon carbide, and rouge (an iron oxide) are used in
loose form over a variety of grain size ranges.
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 9
The prime ingredient for silica refractories, sometimes termed acid refractories, is silica.
These materials, well known for their high-temperature load-bearing capacity, are commonly used
in the arched roofs of steel- and glass-making furnaces; for these applications, temperatures as
high as 1650
0
C (3000
0
F) may be realized. Under these conditions, some small portion of the
brick actually exists as a liquid. The presence of even small concentrations of alumina has an
adverse influence on the performance of these refractories.
These refractory materials are also resistant to slags that are rich in silica (called acid
slags) and are often used as containment vessels for them. However, they are readily attacked
by slags composed of a high proportion of CaO and/or MgO (basic slags), and contact with these
oxide materials should be avoided.
Basic Refractories
The refractories that are rich in periclase, or magnesia (MgO), are termed basic; they may
also contain calcium, chromium, and iron compounds. The presence of silica is deleterious to
their high-temperature performance. Basic refractories are especially resistant to attack by slags
containing high concentrations of MgO and CaO and find extensive use in some steel-making
open hearth furnaces.
Special Refractories
Yet other ceramic materials are used for rather specialized refractory applications. Some
of these are relatively high-purity oxide materials, many of which may be produced with very little
porosity. Included in this group are alumina, silica, magnesia, beryllia (BeO), zirconia (ZrO2), and
mullite (3Al2O3–2SiO2). Others include carbide compounds, in addition to carbon and graphite.
Silicon carbide (SiC) has been used for electrical resistance heating elements, as a crucible
material, and in internal furnace components. Carbon and graphite are very refractory, but find
limited application because they are susceptible to oxidation at temperatures in excess of about
800C (1470F). As would be expected, these specialized refractories are relatively expensive.
ABRASIVES
Abrasive ceramics are used to wear, grind, or cut away other material, which necessarily
is softer. Therefore, the prime requisite for this group of materials is hardness or wear resistance;
in addition, a high degree of toughness is essential to ensure that the abrasive particles do not
easily fracture. Furthermore, high temperatures may be produced from abrasive frictional forces,
so some refractoriness is also desirable. Diamonds, both natural and synthetic, are used as
abrasives; however, they are relatively expensive. The more common ceramic abrasives include
silicon carbide, tungsten carbide (WC), aluminum oxide (or corundum), and silica sand.
Coated abrasives are those in which an abrasive powder is coated on some type of paper
or cloth material; sandpaper is probably the most familiar example. Wood, metals, ceramics, and
plastics are all frequently ground and polished using this form of abrasive. Grinding, lapping, and
polishing wheels often employ loose abrasive grains that are delivered in some type of oil- or
water-based vehicle. Diamonds, corundum, silicon carbide, and rouge (an iron oxide) are used in
loose form over a variety of grain size ranges.
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Module No. 7 – Ceramics 10
CEMENTS
Several familiar ceramic materials are classified as inorganic cements: cement, plaster of
Paris, and lime, which, as a group, are produced in extremely large quantities. The characteristic
feature of these materials is that when mixed with water, they form a paste that subsequently sets
and hardens.
Of this group of materials, Portland cement is consumed in the largest tonnages. It is
produced by grinding and intimately mixing clay and lime-bearing minerals in the proper
proportions and then heating the mixture to about 1400
0
C (2550
0
F) in a rotary kiln; this process,
sometimes called calcination, produces physical and chemical changes in the raw materials. The
resulting “clinker” product is then ground into a very fine powder, to which is added a small amount
of gypsum (CaSO4–2H2O) to retard the setting process. This product is Portland cement. The
properties of Portland cement, including setting time and final strength, to a large degree depend
on its composition.
CARBONS
Diamond
The physical properties of diamond are extraordinary. Chemically, it is very inert and
resistant to attack by a host of corrosive media. Of all known bulk materials, diamond is the
hardest—as a result of its extremely strong interatomic sp
3
bonds. In addition, of all solids, it has
the lowest sliding coefficient of friction. Its thermal conductivity is extremely high, its electrical
properties are notable, and, optically, it is transparent in the visible and infrared regions of the
electromagnetic spectrum—in fact, it has the widest spectral transmission range of all materials.
The high index of refraction and optical brilliance of single crystals makes diamond a most highly
valued gemstone.
Graphite
Graphite is highly anisotropic—property values depend on crystallographic direction along
which they are measured. Graphite is very soft and flaky, and has a significantly smaller modulus
or elasticity. Its in-plane electrical conductivity is 10
16
to 10
19
times that of diamond, whereas
thermal conductivities are approximately the same. Furthermore, whereas the coefficient of
thermal expansion for diamond is relatively small and positive, graphite’s in-plane value is small
and negative, and the plane-perpendicular coefficient is positive and relatively large. Furthermore,
graphite is optically opaque with a black–silver color. Other desirable properties of graphite
include good chemical stability at elevated temperatures and in nonoxidizing atmospheres, high
resistance to thermal shock, high adsorption of gases, and good machinability. Applications for
graphite are many, varied, and include lubricants, pencils, battery electrodes, friction materials
(e.g., brake shoes), heating elements for electric furnaces, welding electrodes, metallurgical
crucibles, high-temperature refractories and insulations, rocket nozzles, chemical reactor vessels,
electrical contacts (e.g., brushes), and air purification devices.
Carbon Fibers
Small-diameter, high-strength, and high-modulus fibers composed of carbon are used as
reinforcements in polymer-matrix composites. Carbon in these fiber materials is in the form of
graphene layers. However, depending on precursor (i.e., material from which the fibers are made)
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 10
CEMENTS
Several familiar ceramic materials are classified as inorganic cements: cement, plaster of
Paris, and lime, which, as a group, are produced in extremely large quantities. The characteristic
feature of these materials is that when mixed with water, they form a paste that subsequently sets
and hardens.
Of this group of materials, Portland cement is consumed in the largest tonnages. It is
produced by grinding and intimately mixing clay and lime-bearing minerals in the proper
proportions and then heating the mixture to about 1400
0
C (2550
0
F) in a rotary kiln; this process,
sometimes called calcination, produces physical and chemical changes in the raw materials. The
resulting “clinker” product is then ground into a very fine powder, to which is added a small amount
of gypsum (CaSO4–2H2O) to retard the setting process. This product is Portland cement. The
properties of Portland cement, including setting time and final strength, to a large degree depend
on its composition.
CARBONS
Diamond
The physical properties of diamond are extraordinary. Chemically, it is very inert and
resistant to attack by a host of corrosive media. Of all known bulk materials, diamond is the
hardest—as a result of its extremely strong interatomic sp
3
bonds. In addition, of all solids, it has
the lowest sliding coefficient of friction. Its thermal conductivity is extremely high, its electrical
properties are notable, and, optically, it is transparent in the visible and infrared regions of the
electromagnetic spectrum—in fact, it has the widest spectral transmission range of all materials.
The high index of refraction and optical brilliance of single crystals makes diamond a most highly
valued gemstone.
Graphite
Graphite is highly anisotropic—property values depend on crystallographic direction along
which they are measured. Graphite is very soft and flaky, and has a significantly smaller modulus
or elasticity. Its in-plane electrical conductivity is 10
16
to 10
19
times that of diamond, whereas
thermal conductivities are approximately the same. Furthermore, whereas the coefficient of
thermal expansion for diamond is relatively small and positive, graphite’s in-plane value is small
and negative, and the plane-perpendicular coefficient is positive and relatively large. Furthermore,
graphite is optically opaque with a black–silver color. Other desirable properties of graphite
include good chemical stability at elevated temperatures and in nonoxidizing atmospheres, high
resistance to thermal shock, high adsorption of gases, and good machinability. Applications for
graphite are many, varied, and include lubricants, pencils, battery electrodes, friction materials
(e.g., brake shoes), heating elements for electric furnaces, welding electrodes, metallurgical
crucibles, high-temperature refractories and insulations, rocket nozzles, chemical reactor vessels,
electrical contacts (e.g., brushes), and air purification devices.
Carbon Fibers
Small-diameter, high-strength, and high-modulus fibers composed of carbon are used as
reinforcements in polymer-matrix composites. Carbon in these fiber materials is in the form of
graphene layers. However, depending on precursor (i.e., material from which the fibers are made)
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Module No. 7 – Ceramics 11
and heat treatment, different structural arrangements of these graphene layers exist. For what
are termed graphitic carbon fibers, the graphene layers assume the ordered structure of
graphite—planes are parallel to one another having relatively weak van der Waals interplanar
bonds.
Because most of these fibers are composed of both graphitic and turbostratic forms, the
term carbon rather than graphite is used to denote these fibers. Of the three most common
reinforcing fiber types used for polymer-reinforced composites (carbon, glass, and aramid),
carbon fibers have the highest modulus of elasticity and strength; in addition, they are the most
expensive.
Table 4. properties of Diamond, Graphite and Carbon (for Fibers)
Adapted from Table 13.3, Callister 9e
ADVANCED CERAMICS
Although the traditional ceramics discussed previously account for the bulk of production,
the development of new and what are termed advanced ceramics has begun and will continue to
establish a prominent niche in advanced technologies. In particular, electrical, magnetic, and
optical properties and property combinations unique to ceramics have been exploited in a host of
new products. Advanced ceramics include materials used in microelectromechanical systems as
well as the nanocarbons (fullerenes, carbon nanotubes, and graphene)
Microelectromechanical Systems (MEMS)
Microelectromechanical systems (abbreviated MEMS) are miniature “smart” systems
consisting of a multitude of mechanical devices that are integrated with large numbers of electrical
elements on a substrate of silicon. The mechanical components are microsensors and micro-
actuators.
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 11
and heat treatment, different structural arrangements of these graphene layers exist. For what
are termed graphitic carbon fibers, the graphene layers assume the ordered structure of
graphite—planes are parallel to one another having relatively weak van der Waals interplanar
bonds.
Because most of these fibers are composed of both graphitic and turbostratic forms, the
term carbon rather than graphite is used to denote these fibers. Of the three most common
reinforcing fiber types used for polymer-reinforced composites (carbon, glass, and aramid),
carbon fibers have the highest modulus of elasticity and strength; in addition, they are the most
expensive.
Table 4. properties of Diamond, Graphite and Carbon (for Fibers)
Adapted from Table 13.3, Callister 9e
ADVANCED CERAMICS
Although the traditional ceramics discussed previously account for the bulk of production,
the development of new and what are termed advanced ceramics has begun and will continue to
establish a prominent niche in advanced technologies. In particular, electrical, magnetic, and
optical properties and property combinations unique to ceramics have been exploited in a host of
new products. Advanced ceramics include materials used in microelectromechanical systems as
well as the nanocarbons (fullerenes, carbon nanotubes, and graphene)
Microelectromechanical Systems (MEMS)
Microelectromechanical systems (abbreviated MEMS) are miniature “smart” systems
consisting of a multitude of mechanical devices that are integrated with large numbers of electrical
elements on a substrate of silicon. The mechanical components are microsensors and micro-
actuators.
E N G G 4 1 2 :
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Module No. 7 – Ceramics 12
The processing of MEMS is virtually the same as that used for the production of silicon-
based integrated circuits; this includes photolithographic, ion implantation, etching, and deposition
technologies, which are well established. In addition, some mechanical components are
fabricated using micromachining techniques. MEMS components are very sophisticated, reliable,
and minuscule in size. Furthermore, because the preceding fabrication techniques involve batch
operations, the MEMS technology is very economical and cost effective. There are some
limitations to the use of silicon in MEMS. Silicon has a low fracture toughness (0.90 MPa1m) and
a relatively low softening temperature (600C) and is highly active to the presence of water and
oxygen. Consequently, research is being conducted into using ceramic materials—which are
tougher, more refractory, and more inert—for some MEMS components, especially high-speed
devices and nanoturbines.
One example of a practical MEMS application is an accelerometer (accelerator/
decelerator sensor) that is used in the deployment of air-bag systems in automobile crashes. For
this application, the important microelectronic component is a free-standing microbeam.
Compared to conventional air-bag systems, the MEMS units are smaller, lighter, and more reliable
and are produced at a considerable cost reduction. Potential MEMS applications include
electronic displays, data storage units, energy conversion devices, chemical detectors (for
hazardous chemical and biological agents and drug screening), and microsystems for DNA
amplification and identification. There are undoubtedly many unforeseen uses of this MEMS
technology that will have a profound impact on society; these will probably overshadow the effects
that microelectronic integrated circuits have had during the past three decades.
Nanocarbons
A class of recently discovered carbon materials, the nanocarbons, have novel and
exceptional properties, are currently being used in some cutting-edge technologies, and will
certainly play an important role in future high-tech applications. Three nanocarbons that belong
to this class are fullerenes, carbon nanotubes, and graphene. The “nano” prefix denotes that the
particle size is less than about 100 nanometers.
Fullerenes
One type of fullerene, discovered in 1985, consists of a hollow spherical cluster of 60
carbon atoms; a single molecule is denoted by C60. Carbon atoms bond together so as to form
both hexagonal (six-carbon atom) and pentagonal (five-carbon atom) geometrical configurations.
Material composed of C60 molecules is known as buckminsterfullerene, (or buckyball for short),
named in honor of R. Buckminster Fuller, who invented the geodesic dome; each C60 is simply
a molecular replica of such a dome. The term fullerene is used to denote the class of materials
that are composed of this type of molecule.
Uses and potential applications of fullerenes include antioxidants in personal care
products, biopharmaceuticals, catalysts, organic solar cells, long-life batteries, high-temperature
superconductors, and molecular magnets.
Carbon Nanotubes
Another molecular form of carbon has recently been discovered that has some unique and
technologically promising properties. Its structure consists of a single sheet of graphite (i.e.,
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 12
The processing of MEMS is virtually the same as that used for the production of silicon-
based integrated circuits; this includes photolithographic, ion implantation, etching, and deposition
technologies, which are well established. In addition, some mechanical components are
fabricated using micromachining techniques. MEMS components are very sophisticated, reliable,
and minuscule in size. Furthermore, because the preceding fabrication techniques involve batch
operations, the MEMS technology is very economical and cost effective. There are some
limitations to the use of silicon in MEMS. Silicon has a low fracture toughness (0.90 MPa1m) and
a relatively low softening temperature (600C) and is highly active to the presence of water and
oxygen. Consequently, research is being conducted into using ceramic materials—which are
tougher, more refractory, and more inert—for some MEMS components, especially high-speed
devices and nanoturbines.
One example of a practical MEMS application is an accelerometer (accelerator/
decelerator sensor) that is used in the deployment of air-bag systems in automobile crashes. For
this application, the important microelectronic component is a free-standing microbeam.
Compared to conventional air-bag systems, the MEMS units are smaller, lighter, and more reliable
and are produced at a considerable cost reduction. Potential MEMS applications include
electronic displays, data storage units, energy conversion devices, chemical detectors (for
hazardous chemical and biological agents and drug screening), and microsystems for DNA
amplification and identification. There are undoubtedly many unforeseen uses of this MEMS
technology that will have a profound impact on society; these will probably overshadow the effects
that microelectronic integrated circuits have had during the past three decades.
Nanocarbons
A class of recently discovered carbon materials, the nanocarbons, have novel and
exceptional properties, are currently being used in some cutting-edge technologies, and will
certainly play an important role in future high-tech applications. Three nanocarbons that belong
to this class are fullerenes, carbon nanotubes, and graphene. The “nano” prefix denotes that the
particle size is less than about 100 nanometers.
Fullerenes
One type of fullerene, discovered in 1985, consists of a hollow spherical cluster of 60
carbon atoms; a single molecule is denoted by C60. Carbon atoms bond together so as to form
both hexagonal (six-carbon atom) and pentagonal (five-carbon atom) geometrical configurations.
Material composed of C60 molecules is known as buckminsterfullerene, (or buckyball for short),
named in honor of R. Buckminster Fuller, who invented the geodesic dome; each C60 is simply
a molecular replica of such a dome. The term fullerene is used to denote the class of materials
that are composed of this type of molecule.
Uses and potential applications of fullerenes include antioxidants in personal care
products, biopharmaceuticals, catalysts, organic solar cells, long-life batteries, high-temperature
superconductors, and molecular magnets.
Carbon Nanotubes
Another molecular form of carbon has recently been discovered that has some unique and
technologically promising properties. Its structure consists of a single sheet of graphite (i.e.,
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Module No. 7 – Ceramics 13
graphene) that is rolled into a tube. The term single-walled carbon nanotube (abbreviated
SWCNT) is used to denote this structure. Each nanotube is a single molecule composed of
millions of atoms; the length of this molecule is much greater (on the order of thousands of times
greater) than its diameter. Multiple-walled carbon nanotubes (MWCNTs) consisting of concentric
cylinders also exist.
Nanotubes are extremely strong and stiff and relatively ductile. For single-walled
nanotubes, measured tensile strengths range between 13 and 53 GPa (approximately an order
of magnitude greater than for carbon fibers—viz. 2 to 6 GPa); this is one of the strongest known
materials. Elastic modulus values are on the order of one terapascal [TPa (1 TPa =10
3
GPa)],
with fracture strains between about 5% and 20%. Furthermore, nanotubes have relatively low
densities.
Carbon nanotubes also have unique and structure-sensitive electrical characteristics.
Depending on the orientation of the hexagonal units in the graphene plane (i.e., tube wall) with
the tube axis, the nanotube may behave electrically as either a metal or a semiconductor. As a
metal, they have the potential for use as wiring for small-scale circuits. In the semiconducting
state they may be used for transistors and diodes. Furthermore, nanotubes are excellent electric
field emitters. As such, they can be used for flat-screen displays (e.g., television screens and
computer monitors).
Graphene
Graphene, the newest member of the nanocarbons, is a single-atomic-layer of graphite,
composed of hexagonally sp2 bonded carbon atoms (Figure 13.9). These bonds are extremely
strong, yet flexible, which allows the sheets to bend.
Two characteristics of graphene make it an exceptional material. First is the perfect order
found in its sheets—no atomic defects such as vacancies exist; also these sheets are extremely
pure—only carbon atoms are present. The second characteristic relates to the nature of the
unbonded electrons: at room temperature, they move much faster than conducting electrons in
ordinary metals and semiconducting materials.
In terms of its properties graphene could be labeled the ultimate material. It is the strongest
known material (~130 GPa), the best thermal conductor (~5000 W/mK), and has the lowest
electrical resistivity (10
-8
Ωm)—that is, is the best electrical conductor. Furthermore, it is
transparent, chemically inert, and has a modulus of elasticity comparable to the other
nanocarbons (~1 TPa).
Given this set of properties, the technological potential for graphene is enormous, and it
is expected to revolutionize many industries to include electronics, energy, transportation,
medicine/biotechnology, and aeronautics. However, before this revolution can begin to be
realized, economical and reliable methods for the mass production of graphene must be devised.
The following is a short list of some of these potential applications for graphene: electronics—
touch-screens, conductive ink for electronic printing, transparent conductors, transistors, heat
sinks; energy—polymer solar cells, catalysts in fuel cells, battery electrodes, supercapacitors;
medicine/biotechnology—artificial muscle, enzyme and DNA biosensors, photoimaging;
aeronautics—chemical sensors (for explosives) and nanocomposites for aircraft structural
components.
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 13
graphene) that is rolled into a tube. The term single-walled carbon nanotube (abbreviated
SWCNT) is used to denote this structure. Each nanotube is a single molecule composed of
millions of atoms; the length of this molecule is much greater (on the order of thousands of times
greater) than its diameter. Multiple-walled carbon nanotubes (MWCNTs) consisting of concentric
cylinders also exist.
Nanotubes are extremely strong and stiff and relatively ductile. For single-walled
nanotubes, measured tensile strengths range between 13 and 53 GPa (approximately an order
of magnitude greater than for carbon fibers—viz. 2 to 6 GPa); this is one of the strongest known
materials. Elastic modulus values are on the order of one terapascal [TPa (1 TPa =10
3
GPa)],
with fracture strains between about 5% and 20%. Furthermore, nanotubes have relatively low
densities.
Carbon nanotubes also have unique and structure-sensitive electrical characteristics.
Depending on the orientation of the hexagonal units in the graphene plane (i.e., tube wall) with
the tube axis, the nanotube may behave electrically as either a metal or a semiconductor. As a
metal, they have the potential for use as wiring for small-scale circuits. In the semiconducting
state they may be used for transistors and diodes. Furthermore, nanotubes are excellent electric
field emitters. As such, they can be used for flat-screen displays (e.g., television screens and
computer monitors).
Graphene
Graphene, the newest member of the nanocarbons, is a single-atomic-layer of graphite,
composed of hexagonally sp2 bonded carbon atoms (Figure 13.9). These bonds are extremely
strong, yet flexible, which allows the sheets to bend.
Two characteristics of graphene make it an exceptional material. First is the perfect order
found in its sheets—no atomic defects such as vacancies exist; also these sheets are extremely
pure—only carbon atoms are present. The second characteristic relates to the nature of the
unbonded electrons: at room temperature, they move much faster than conducting electrons in
ordinary metals and semiconducting materials.
In terms of its properties graphene could be labeled the ultimate material. It is the strongest
known material (~130 GPa), the best thermal conductor (~5000 W/mK), and has the lowest
electrical resistivity (10
-8
Ωm)—that is, is the best electrical conductor. Furthermore, it is
transparent, chemically inert, and has a modulus of elasticity comparable to the other
nanocarbons (~1 TPa).
Given this set of properties, the technological potential for graphene is enormous, and it
is expected to revolutionize many industries to include electronics, energy, transportation,
medicine/biotechnology, and aeronautics. However, before this revolution can begin to be
realized, economical and reliable methods for the mass production of graphene must be devised.
The following is a short list of some of these potential applications for graphene: electronics—
touch-screens, conductive ink for electronic printing, transparent conductors, transistors, heat
sinks; energy—polymer solar cells, catalysts in fuel cells, battery electrodes, supercapacitors;
medicine/biotechnology—artificial muscle, enzyme and DNA biosensors, photoimaging;
aeronautics—chemical sensors (for explosives) and nanocomposites for aircraft structural
components.
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Module No. 7 – Ceramics 14
Table 5. Properties of Nanocarbon
Adapted from Table 13.4, Callister 9e
Fabrication and Processing of Ceramics
Because ceramic materials have relatively high melting temperatures, casting them is
normally impractical. Furthermore, in most instances the brittleness of these materials precludes
deformation. Some ceramic pieces are formed from powders (or particulate collections) that must
ultimately be dried and fired. Glass shapes are formed at elevated temperatures from a fluid mass
that becomes very viscous upon cooling. Cements are shaped by placing into forms a fluid paste
that hardens and assumes a permanent set by virtue of chemical reactions. A taxonomical
scheme for the several types of ceramic-forming techniques is presented in Figure 13.10.
Figure 7. Classification Scheme for the ceramic-forming technique.
Adapted from Figure 13.10, Callister 9e
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 14
Table 5. Properties of Nanocarbon
Adapted from Table 13.4, Callister 9e
Fabrication and Processing of Ceramics
Because ceramic materials have relatively high melting temperatures, casting them is
normally impractical. Furthermore, in most instances the brittleness of these materials precludes
deformation. Some ceramic pieces are formed from powders (or particulate collections) that must
ultimately be dried and fired. Glass shapes are formed at elevated temperatures from a fluid mass
that becomes very viscous upon cooling. Cements are shaped by placing into forms a fluid paste
that hardens and assumes a permanent set by virtue of chemical reactions. A taxonomical
scheme for the several types of ceramic-forming techniques is presented in Figure 13.10.
Figure 7. Classification Scheme for the ceramic-forming technique.
Adapted from Figure 13.10, Callister 9e
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Module No. 7 – Ceramics 15
Glass Forming
Glass is produced by heating the raw materials to an elevated temperature above which
melting occurs. Most commercial glasses are of the silica-soda-lime variety; the silica is usually
supplied as common quartz sand, whereas Na2O and CaO are added as soda ash (Na2CO3) and
limestone (CaCO3). For most applications, especially when optical transparency is important, it is
essential that the glass product be homogeneous and pore free. Homogeneity is achieved by
complete melting and mixing of the raw ingredients. Porosity results from small gas bubbles that
are produced; these must be absorbed into the melt or otherwise eliminated, which requires
proper adjustment of the viscosity of the molten material.
Different forming methods are used to fabricate glass products:
Pressing
Pressing is used in the fabrication of relatively thick-walled pieces such as plates and
dishes. The glass piece is formed by pressure application in a graphite-coated cast iron mold
having the desired shape; the mold is typically heated to ensure an even surface.
Blowing
Although some glass blowing is done by hand, especially for art objects, the process
has been completely automated for the production of glass jars, bottles, and light bulbs. From a
raw gob of glass, a parison, or temporary shape, is formed by mechanical pressing in a mold.
This piece is inserted into a finishing or blow mold and forced to conform to the mold contours by
the pressure created from a blast of air
Drawing
Drawing is used to form long glass pieces that have a constant cross section, such as
sheet, rod, tubing, and fibers
Figure 8. The press and blow method for producing a glass bottle.
Adapted from C. J. Phillips, Glass: The Miracle Maker. Reproduced by permission of Pitman
Publishing Ltd., London
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 15
Glass Forming
Glass is produced by heating the raw materials to an elevated temperature above which
melting occurs. Most commercial glasses are of the silica-soda-lime variety; the silica is usually
supplied as common quartz sand, whereas Na2O and CaO are added as soda ash (Na2CO3) and
limestone (CaCO3). For most applications, especially when optical transparency is important, it is
essential that the glass product be homogeneous and pore free. Homogeneity is achieved by
complete melting and mixing of the raw ingredients. Porosity results from small gas bubbles that
are produced; these must be absorbed into the melt or otherwise eliminated, which requires
proper adjustment of the viscosity of the molten material.
Different forming methods are used to fabricate glass products:
Pressing
Pressing is used in the fabrication of relatively thick-walled pieces such as plates and
dishes. The glass piece is formed by pressure application in a graphite-coated cast iron mold
having the desired shape; the mold is typically heated to ensure an even surface.
Blowing
Although some glass blowing is done by hand, especially for art objects, the process
has been completely automated for the production of glass jars, bottles, and light bulbs. From a
raw gob of glass, a parison, or temporary shape, is formed by mechanical pressing in a mold.
This piece is inserted into a finishing or blow mold and forced to conform to the mold contours by
the pressure created from a blast of air
Drawing
Drawing is used to form long glass pieces that have a constant cross section, such as
sheet, rod, tubing, and fibers
Figure 8. The press and blow method for producing a glass bottle.
Adapted from C. J. Phillips, Glass: The Miracle Maker. Reproduced by permission of Pitman
Publishing Ltd., London
E N G G 4 1 2 :
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 16
Figure 9. Schematic diagram showing the float process for making glass.
Source: Pilkington Group Limited
FABRICATION AND PROCESSING OF CLAY PRODUCTS
The as-mined raw materials usually have to go through a milling or grinding operation in
which particle size is reduced; this is followed by screening or sizing to yield a powdered product
having a desired range of particle sizes. For multicomponent systems, powders must be
thoroughly mixed with water and perhaps other ingredients to give flow characteristics that are
compatible with the particular forming technique. The formed piece must have sufficient
mechanical strength to remain intact during transporting, drying, and firing operations. Two
common shaping techniques are used to form clay-based compositions: hydroplastic forming and
slip casting.
Hydroplastic Forming
The most common hydroplastic forming technique is extrusion, in which a stiff plastic
ceramic mass is forced through a die orifice having the desired cross-sectional geometry; it is
similar to the extrusion of metals. Brick, pipe, ceramic blocks, and tiles are all commonly fabricated
using hydroplastic forming. Usually the plastic ceramic is forced through the die by means of a
motor-driven auger, and often air is removed in a vacuum chamber to enhance the density. Hollow
internal columns in the extruded piece (e.g., building brick) are formed by inserts situated within
the die.
Slip Casting
Another forming process used for clay-based compositions is slip casting. A slip is a
suspension of clay and/or other nonplastic materials in water. When poured into a porous mold
(commonly made of plaster of Paris), water from the slip is absorbed into the mold, leaving behind
a solid layer on the mold wall, the thickness of which depends on the time. This process may be
continued until the entire mold cavity becomes solid (solid casting). Alternatively, it may be
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 16
Figure 9. Schematic diagram showing the float process for making glass.
Source: Pilkington Group Limited
FABRICATION AND PROCESSING OF CLAY PRODUCTS
The as-mined raw materials usually have to go through a milling or grinding operation in
which particle size is reduced; this is followed by screening or sizing to yield a powdered product
having a desired range of particle sizes. For multicomponent systems, powders must be
thoroughly mixed with water and perhaps other ingredients to give flow characteristics that are
compatible with the particular forming technique. The formed piece must have sufficient
mechanical strength to remain intact during transporting, drying, and firing operations. Two
common shaping techniques are used to form clay-based compositions: hydroplastic forming and
slip casting.
Hydroplastic Forming
The most common hydroplastic forming technique is extrusion, in which a stiff plastic
ceramic mass is forced through a die orifice having the desired cross-sectional geometry; it is
similar to the extrusion of metals. Brick, pipe, ceramic blocks, and tiles are all commonly fabricated
using hydroplastic forming. Usually the plastic ceramic is forced through the die by means of a
motor-driven auger, and often air is removed in a vacuum chamber to enhance the density. Hollow
internal columns in the extruded piece (e.g., building brick) are formed by inserts situated within
the die.
Slip Casting
Another forming process used for clay-based compositions is slip casting. A slip is a
suspension of clay and/or other nonplastic materials in water. When poured into a porous mold
(commonly made of plaster of Paris), water from the slip is absorbed into the mold, leaving behind
a solid layer on the mold wall, the thickness of which depends on the time. This process may be
continued until the entire mold cavity becomes solid (solid casting). Alternatively, it may be
E N G G 4 1 2 :
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 17
terminated when the solid shell wall reaches the desired thickness, by inverting the mold and
pouring out the excess slip; this is termed drain casting (Figure 13.17b). As the cast piece dries
and shrinks, it pulls away (or releases) from the mold wall; at this time, the mold may be
disassembled and the cast piece removed.
Drying and Firing
A ceramic piece that has been formed hydroplastically or by slip casting retains significant
porosity and has insufficient strength for most practical applications. In addition, it may still contain
some of the liquid (e.g., water) that was added to assist in the forming operation. This liquid is
removed in a drying process; density and strength are enhanced as a result of a high-temperature
heat treatment or firing procedure. A body that has been formed and dried but not fired is termed
green. Drying and firing techniques are critical inasmuch as defects that ordinarily render the ware
useless (e.g., warpage, distortion, cracks) may be introduced during the operation. These defects
normally result from stresses that are set up from nonuniform shrinkage.
Drying
As a clay-based ceramic body dries, it also experiences some shrinkage. In the early
stages of drying, the clay particles are virtually surrounded by and separated from one another
by a thin film of water. As drying progresses and water is removed, the interparticle separation
decreases, which is manifested as shrinkage.
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 17
terminated when the solid shell wall reaches the desired thickness, by inverting the mold and
pouring out the excess slip; this is termed drain casting (Figure 13.17b). As the cast piece dries
and shrinks, it pulls away (or releases) from the mold wall; at this time, the mold may be
disassembled and the cast piece removed.
Drying and Firing
A ceramic piece that has been formed hydroplastically or by slip casting retains significant
porosity and has insufficient strength for most practical applications. In addition, it may still contain
some of the liquid (e.g., water) that was added to assist in the forming operation. This liquid is
removed in a drying process; density and strength are enhanced as a result of a high-temperature
heat treatment or firing procedure. A body that has been formed and dried but not fired is termed
green. Drying and firing techniques are critical inasmuch as defects that ordinarily render the ware
useless (e.g., warpage, distortion, cracks) may be introduced during the operation. These defects
normally result from stresses that are set up from nonuniform shrinkage.
Drying
As a clay-based ceramic body dries, it also experiences some shrinkage. In the early
stages of drying, the clay particles are virtually surrounded by and separated from one another
by a thin film of water. As drying progresses and water is removed, the interparticle separation
decreases, which is manifested as shrinkage.
E N G G 4 1 2 :
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 18
Firing
After drying, a body is usually fired at a temperature between 900
0
C and 1400
0
C (1650
0
F
and 2550
0
F); the firing temperature depends on the composition and desired properties of the
finished piece. During the firing operation, the density is further increased (with an attendant
decrease in porosity) and the mechanical strength is enhanced.
POWDER PRESSING
Another important and commonly used method that warrants brief treatment is powder
pressing. Powder pressing—the ceramic analogue to powder metallurgy—is used to fabricate
both clay and nonclay compositions, including electronic and magnetic ceramics, as well as some
refractory brick products. In essence, a powdered mass, usually containing a small amount of
water or other binder, is compacted into the desired shape by pressure. The degree of compaction
is maximized and the fraction of void space is minimized by using coarse and fine particles mixed
in appropriate proportions. There is no plastic deformation of the particles during compaction, as
there may be with metal powders.
There are three basic powder-pressing procedures: uniaxial, isostatic (or hydrostatic), and
hot pressing.
1. For uniaxial pressing, the powder is compacted in a metal die by pressure that is applied
in a single direction. The formed piece takes on the configuration of the die and platens through
which the pressure is applied. This method is confined to shapes that are relatively simple;
however, production rates are high and the process is inexpensive.
2. For isostatic pressing, the powdered material is contained in a rubber envelope and the
pressure is applied isostatically by a fluid (i.e., it has the same magnitude in all directions). More
complicated shapes are possible than with uniaxial pressing; however, the isostatic technique is
more time consuming and expensive. For both uniaxial and isostatic procedures, a firing operation
is required after the pressing operation. During firing the formed piece shrinks and experiences a
reduction of porosity and an improvement in mechanical integrity.
3. With hot pressing, the powder pressing and heat treatment are performed
simultaneously—the powder aggregate is compacted at an elevated temperature. The procedure
is used for materials that do not form a liquid phase except at very high and impractical
temperatures; in addition, it is used when high densities without appreciable grain growth are
desired. This is an expensive fabrication technique and has some limitations. It is costly in terms
of time, because both mold and die must be heated and cooled during each cycle. In addition, the
mold is usually expensive to fabricate and typically has a short lifetime.
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 18
Firing
After drying, a body is usually fired at a temperature between 900
0
C and 1400
0
C (1650
0
F
and 2550
0
F); the firing temperature depends on the composition and desired properties of the
finished piece. During the firing operation, the density is further increased (with an attendant
decrease in porosity) and the mechanical strength is enhanced.
POWDER PRESSING
Another important and commonly used method that warrants brief treatment is powder
pressing. Powder pressing—the ceramic analogue to powder metallurgy—is used to fabricate
both clay and nonclay compositions, including electronic and magnetic ceramics, as well as some
refractory brick products. In essence, a powdered mass, usually containing a small amount of
water or other binder, is compacted into the desired shape by pressure. The degree of compaction
is maximized and the fraction of void space is minimized by using coarse and fine particles mixed
in appropriate proportions. There is no plastic deformation of the particles during compaction, as
there may be with metal powders.
There are three basic powder-pressing procedures: uniaxial, isostatic (or hydrostatic), and
hot pressing.
1. For uniaxial pressing, the powder is compacted in a metal die by pressure that is applied
in a single direction. The formed piece takes on the configuration of the die and platens through
which the pressure is applied. This method is confined to shapes that are relatively simple;
however, production rates are high and the process is inexpensive.
2. For isostatic pressing, the powdered material is contained in a rubber envelope and the
pressure is applied isostatically by a fluid (i.e., it has the same magnitude in all directions). More
complicated shapes are possible than with uniaxial pressing; however, the isostatic technique is
more time consuming and expensive. For both uniaxial and isostatic procedures, a firing operation
is required after the pressing operation. During firing the formed piece shrinks and experiences a
reduction of porosity and an improvement in mechanical integrity.
3. With hot pressing, the powder pressing and heat treatment are performed
simultaneously—the powder aggregate is compacted at an elevated temperature. The procedure
is used for materials that do not form a liquid phase except at very high and impractical
temperatures; in addition, it is used when high densities without appreciable grain growth are
desired. This is an expensive fabrication technique and has some limitations. It is costly in terms
of time, because both mold and die must be heated and cooled during each cycle. In addition, the
mold is usually expensive to fabricate and typically has a short lifetime.
E N G G 4 1 2 :
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 19
TAPE CASTING
Tape casting is an important ceramic fabrication technique. As the name implies, in this
technique, thin sheets of a flexible tape are produced by means of a casting process. These
sheets are prepared from slips in many respects similar to those employed for slip This type of
slip consists of a suspension of ceramic particles in an organic liquid that also contains binders
and plasticizers, which are incorporated to impart strength and flexibility to the cast tape. De-airing
in a vacuum may also be necessary to remove any entrapped air or solvent vapor bubbles, which
may act as crack initiation sites in the finished piece. The actual tape is formed by pouring the slip
onto a flat surface (of stainless steel, glass, a polymeric film, or paper); a doctor blade spreads
the slip into a thin tape of uniform thickness. In the drying process, volatile slip components are
removed by evaporation; this green product is a flexible tape that may be cut or into which holes
may be punched prior to a firing operation. Tape thicknesses normally range between 0.1 and 2
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 19
TAPE CASTING
Tape casting is an important ceramic fabrication technique. As the name implies, in this
technique, thin sheets of a flexible tape are produced by means of a casting process. These
sheets are prepared from slips in many respects similar to those employed for slip This type of
slip consists of a suspension of ceramic particles in an organic liquid that also contains binders
and plasticizers, which are incorporated to impart strength and flexibility to the cast tape. De-airing
in a vacuum may also be necessary to remove any entrapped air or solvent vapor bubbles, which
may act as crack initiation sites in the finished piece. The actual tape is formed by pouring the slip
onto a flat surface (of stainless steel, glass, a polymeric film, or paper); a doctor blade spreads
the slip into a thin tape of uniform thickness. In the drying process, volatile slip components are
removed by evaporation; this green product is a flexible tape that may be cut or into which holes
may be punched prior to a firing operation. Tape thicknesses normally range between 0.1 and 2
E N G G 4 1 2 :
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 20
mm (0.004 and 0.08 in.). Tape casting is widely used in the production of ceramic substrates that
are used for integrated circuits and for multilayered capacitors.
Cementation
Cementation is also considered a ceramic fabrication process. The cement material, when
mixed with water, forms a paste that, after being fashioned into a desired shape, subsequently
hardens as a result of complex chemical reactions.
Reference:
Materials Science and Engineering: An Introduction, 9th Edition, William D. Callister, Jr.
Department of Metallurgical Engineering The University of Utah with special contributions by
David G. Rethwisch The University of Iowa.
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 20
mm (0.004 and 0.08 in.). Tape casting is widely used in the production of ceramic substrates that
are used for integrated circuits and for multilayered capacitors.
Cementation
Cementation is also considered a ceramic fabrication process. The cement material, when
mixed with water, forms a paste that, after being fashioned into a desired shape, subsequently
hardens as a result of complex chemical reactions.
Reference:
Materials Science and Engineering: An Introduction, 9th Edition, William D. Callister, Jr.
Department of Metallurgical Engineering The University of Utah with special contributions by
David G. Rethwisch The University of Iowa.
E N G G 4 1 2 :
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 21
CHAPTER TEST
1. Name the different types of traditional pottery and briefly describe each one of them.
2. List down the major classification of ceramics and give examples of each.
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 21
CHAPTER TEST
1. Name the different types of traditional pottery and briefly describe each one of them.
2. List down the major classification of ceramics and give examples of each.
E N G G 4 1 2 :
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 22
3. Enumerate all ceramic fabrication methods and briefly describe the procedures involved.
4. Cite several applications of ceramics in the field of engineering.
M A T E R I A L S S C I E N C E A N D E N G I N E E R I N G
Module No. 7 – Ceramics 22
3. Enumerate all ceramic fabrication methods and briefly describe the procedures involved.
4. Cite several applications of ceramics in the field of engineering.
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