Ceramics

Callister: Chapters 12, 13 Structure, Properties, Applications and Processing Techniques of:
Silicates Glass - Ceramics Traditional Ceramics Advanced (Engineering) Ceramics

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Ceramics
Ceramics are compounds of metallic and non-metallic elements bonded ionically (some are partially covalent). This type of atomic bonding means that most ceramics have:
High Youngs Modulus High Melting Point Low C.T.E. Strong (high yield strength) Brittle

Very low ductility means that ceramics are very sensitive to internal cracks and flaws

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Crystal Structure
Since ceramics are comprised of at least two elements, their crystal structures are often more complicated than metals. How the cations (+ve) and anions (-ve) fit together depends on:

1. Maintaining electrical neutrality

according to the chemical formula (e.g. NaCl, Al2O3, )

2. The relative sizes of the ions

Stable structures require that the anions and cations touch

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Coordination Numbers
Linear

Triangular The cations coordination number depends on the ratio of the radii: Tetrahedral

rc ra
Octahedral

Cubic
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AX Crystal Structures
NaCl (Rock Salt) structure The Rock Salt structure is formed from two, interwoven FCC structures. The coordination number of both ions is 6 (octahedral) Other common ceramics with this structure: MgO, MnS, LiF, FeO

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AX Crystal Structures
Cesium Chloride structure The CsCl structure is based on the BCC structure. It is not BCC because two different atoms are involved) The coordination number of both ions is 8 (cubic)

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AX Crystal Structures
Zinc Blende (ZnS) structure The Zinc Blende structure is an FCC-based lattice with zinc anions in 4 of the eight tetrahedral sites The coordination number of both ions is 4 (tetrahedral) Other common ceramics with this structure: ZnTe, SiC

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Silicate Ceramics
The bulk of soils, rocks, clays, and sand are silicate ceramics Silica (SiO2) is a covalently bonded tetrahedral molecule
The bonds are directional and strong.

Rather than discussing unit cells, silicates are described according to the arrangement of the SiO 4 tetrahedra. 4
They can form one-, two-, and three-dimensional structures

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Crystalline Silica
Silica (SiO2) is the simplest of the silicates It is a three-dimensional network formed when every oxygen atom is shared by two, adjacent tetrahedra

Electrical neutrality is maintained (Si:O = 1:2)

There are three polymorphs of crystalline silica

Quartz, cristobalite, and tridymite Neither form is closed packed Density of silica is low.
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Silica Glasses
If molten silica is cooled relatively quickly, it is possible to prevent the formation of a crystalline structure. Fused Silica is still made up of the SiO4 tetrahedra, but not all oxygen atoms are shared between two tetrahedra.
There is short-range, but not long-range order.

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Silica Glasses
To change the properties of the glass, other oxides are often added. Network Formers fit in with the SiO2 tetrahedra. They are added to change the properties of the solidified glass.
e.g. 12% B2O3 is added to silica to make Pyrex. The addition lowers the forming temperature without changing the thermal expansion coefficient.

Network Modifiers do not fit in with the silica network. They make it easier to form a glass (as opposed to crystalline silica).
e.g. most glass (windows, food containers,) contain up to 15% Na2O to make it easier to form a glass

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The Silicates
Depending on how many oxygen atoms are shared, silicates can form a wide variety of structures. Additional cations are often required to maintain charge neutrality (e.g. Ca2+, Mg2+, Al3+) Clays are layered silicates.
Each sheet is covalently bound together, but adjacent sheets are weakly bound by van der Waals forces

Just add water

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Carbon

Carbon exists in a variety of forms:

Diamond Graphite Fullerenes

The different forms have very different properties because they have different structures.

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Diamond
Diamond Cubic crystal structure (similar to zinc blende) Each carbon atom is covalently bonded to 4 others in a tetrahedron.
Very hard/strong Low electrical conductivity High thermal conductivity

Most industrial quality diamond is man-made.

Knives, machine tools, etc.

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Graphite
Graphite has a layered structure. Each atom is covalently bonded to three others in the layer. The fourth bonding electron contributes to van der Waals bonding between the layers. The properties of graphite are directional.

Strong
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Weak

Weak
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Fullerenes
Named after R. Buckminster Fuller, inventor of the geodesic dome. Two forms discovered so far C60, Buckyballs
Again, three covalent and one van der Waals bond

C60 molecules pack together in an FCC arrangement Carbon Nanotubes

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Strength of Ceramics
Material 4340 Steel 2024 Aluminum Ti-6Al-4V Al2O3 Si3N4 Fracture Toughness KIC 99 MPam 26 MPam 55 MPam 1.7 MPam 5 MPam

Very low fracture toughness of ceramics means that failure is almost always due to flaws in the part. Therefore, the design strengths of ceramic materials are described using statistics.

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Fracture Statistics

Nominally identical samples may fail at very different stresses

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Three-Point Bend Test

It is difficult to perform tensile tests on brittle materials.
They often crush in the grips.

The three-point bend test avoids this problem, but has its own drawbacks The maximum tensile stress is only seen by the material on the bottom surface, directly under the plunger.

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Three-Point Bend Test

The results from a 3-point bend test appear similar to those from a tensile test. These particular results illustrate the effect that structure has on properties:
Crystalline Al2O3 is stiffer and stronger than amorphous glass

Note the very small strains

0.2% is not even on the scale!

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Three-Point Bend Test

The stress is calculated according to the formula shown for a rectangular cross-section The fracture stress determined in this test is known as: Flexural Strength Modulus of Rupture The flexural strength is often higher than the tensile strength Statistics: The biggest flaw may not see the highest stress
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Processing Ceramics
All ceramics have short-range atomic order, some have longrange order.
Crystalline ceramics have short and long-range order Glasses have short-range order Ceramic-glasses have a combination of crystalline and glassy components

Deformation of crystalline ceramics is due to dislocation motion, HOWEVER: The complex crystal structure and strong atomic bonding make dislocation motion exceedingly difficult.

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Processing Glasses
Deformation of non-crystalline ceramics is due to Viscous Flow

F A = = dv dv dy dy

Viscosity is a measure of how difficult it is to shear (e.g. stir) a liquid. Water has a low viscosity Molasses has a high viscosity
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Processing Glasses
When a crystalline material solidifies, there is a step change in volume at the melting temperature. Glasses do not really solidify in the traditional sense. The molecules pack closer and closer together, becoming an increasingly denser liquid. The slight change in slope occurs when the molecules are essentially unable to flow. This is the Glass Transition Temperature.
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Liquid Specific Volume

Temperature

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Ceramic Glasses
Strain Point
Brittle

Annealing Point
Residual stresses removed

Softening point
Can be handled without deformation

Working Point
Easily deformable

Melting Point
True liquid
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Fabricating Glasses

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Fabricating Glasses
How do you get perfectly flat, parallel sided plate glass for windows? The molten glass is floated on top of molten tin (Tm =231C)

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Tempered Glass

The fracture properties of glass can be altered by

Laminating Tempering

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Tempered Glass

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Clay Products
Clay is an aluminosilicate (i.e. Al2O3 and SiO2) with a variety of impurities (usually various other oxides) Common clay products include:
Building bricks, tiles, sewer pipes Pottery, porcelain, china

Clay products are made from various proportions of:

Clay and a flux material (e.g feldspar)
Sheet silicate structure

Filler materials (typically crushed quartz)

Crystalline

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Fabricating Clay Products

Clay is mixed with water to form a plastic body and formed to the desired shape The wet body is then dried and fired.
Drying removes water from the clay a controlled rate Firing vitrifies the clay (turns it into a glass) Degree of vitrification depends on firing temperature

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Microstructure of Clay Products

Crystalline particles surrounded by a glassy matrix with some pores

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Fabricating Crystalline Ceramics

The melting temperature of most ceramics is too high for casting to be a practical option. Engineering ceramics in general are made from powders
Powders are compacted / consolidated to form a green body
Methods include various pressing techniques and tape casting.

The green body is then sintered at elevated temperatures (often under pressure) to bond the powders

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Microstructure of Crystalline Ceramics

Sintered crystalline grains with porosity

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Properties of Crystalline Ceramics

Crystalline ceramics are the Engineering ceramics
High melting points Strong Hard Brittle Good corrosion resistance

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Properties of Glasses
Like crystalline ceramics, glasses are
hard, brittle corrosion resistant

Unlike crystalline ceramics, glasses:

lower melting temperatures can be easily deformed at high temperatures

are not porous

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Properties of Clay Products

Clay products are:
Hard Brittle Corrosion resistant They generally have some porosity, but this can be minimized by increasing the firing temperature Their high temperature creep properties are better than glasses but not as good as crystalline ceramics.

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