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
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:
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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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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
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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
Carbon
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
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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
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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
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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
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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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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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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
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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
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The green body is then sintered at elevated temperatures (often under pressure) to bond the powders
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Properties of Glasses
Like crystalline ceramics, glasses are
hard, brittle corrosion resistant
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