Ceramics

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Ceramics
An inorganic compound consisting of a metal (or semi-metal) and one or more nonmetals Important examples:
Silica - silicon dioxide (SiO2), the main ingredient in most glass products Alumina - aluminum oxide (Al2O3), used in various applications from abrasives to artificial bones Hydrous aluminum silicate (Al2Si2O5(OH)4) - more complex compounds such as the main ingredient in most clay products
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Ceramic Phase Diagrams

MgO-Al2O3 diagram:

Adapted from Fig. 10.24, Callister & Rethwisch 3e.

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Properties of Ceramic Materials

High hardness, electrical and thermal insulating, chemical stability, and high melting temperatures Brittle, virtually no ductility - can cause problems in both processing and performance of ceramic products Some ceramics are translucent, window glass (based on silica) being the clearest example
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Categories of Ceramics
1. Traditional ceramics - clay products such as pottery, bricks, common abrasives, and cement 2. New (advanced) ceramics - more recently developed ceramics based on oxides, carbides, etc., with better mechanical or physical properties than traditional ceramics 3. Glasses - based primarily on silica and distinguished by their noncrystalline structure
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Classification of Ceramics
Ceramic Materials
Glasses Clay Refractories products Abrasives Cements New ceramics

-optical -whiteware -bricks for -sandpaper -composites -engine -composite -structural high T -cutting -structural rotors (furnaces) -polishing reinforce valves -containers/ bearings Adapted from Fig. 13.7 and discussion in -sensors household Section 13.4-10, Callister & Rethwisch 3e.

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Why So Much SiO2 in Glass?

Because SiO2 is the best glass former
Silica is the main component in glass products, usually comprising 50% to 75% of total chemistry It naturally transforms into a glassy state upon cooling from the liquid, whereas most ceramics crystallize upon solidification

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Other Ingredients in Glass

Sodium oxide (Na2O) Calcium oxide (CaO) Aluminum oxide (Al2O3) Magnesium oxide (MgO) Potassium oxide (K2O) Lead oxide (PbO) Boron oxide (B2O3)
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Glass Additives
Act as flux (promoting fusion) during heating Increase fluidity in molten glass for processing Improve chemical resistance against attack by acids, basic substances, or water Add color Alter index of refraction for optics

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Silicate Ceramics
Most common elements in earths crust are Si & O

Si4+ O2Adapted from Figs. 3.10-11, Callister & Rethwisch 3e

crystobalite

SiO44- tetrahedron used to describe crystal structure SiO2 (silica) polymorphic forms are quartz, crystobalite, & tridymite The strong Si-O bonds lead to a high melting temperature (1710C) for this material (important for casting)
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Glass Structure
Basic Unit:

4Si0 4 tetrahedron
Si 4+ O2 -

Glass is noncrystalline (amorphous) Fused silica is SiO2 to which no impurities have been added Other common glasses contain impurity ions such as Na+, Ca2+, Al3+, and B3+

Quartz is crystalline SiO2: corner oxygen atoms shared

Na + Si 4+ O2 -

(soda glass)
Adapted from Fig. 3.41, Callister & Rethwisch 3e. 10/7/2013 ME/IE 380 - Abiade 11

Silicates
Bonding of adjacent SiO44- accomplished by the sharing of common corners, edges, or faces

Mg2SiO4

Ca2MgSi2O7

Adapted from Fig. 3.12, Callister & Rethwisch 3e.

Presence of cations such as Ca2+, Mg2+, & Al3+ 1. maintain charge neutrality, and 2. ionically bond SiO44- to one another
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Layered Silicates
Layered silicates (e.g., clays, mica, talc)
SiO4 tetrahedra connected together to form 2-D plane

A net negative charge is associated with each (Si2O5)2- unit Negative charge balanced by adjacent plane rich in positively charged cations Second planar sheet has excess cations Bonding within the sheets is strong & intermediate ionic/covalent Adjacent sheets loosely bound to each other by weak physical bonds
Adapted from Fig. 3.13, Callister & Rethwisch 3e. 10/7/2013 ME/IE 380 - Abiade 13

 Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+ layer

Layered Silicates (cont)

Adapted from Fig. 3.14, Callister & Rethwisch 3e.

Note: Adjacent sheets of this type are loosely bound to one another by van der Waals forces.
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Mechanical Properties of Ceramics

Theoretically, the strength of ceramics should be higher than metals because their covalent and ionic bonding types are stronger than metallic bonding But metallic bonding allows for slip, the mechanism by which metals deform plastically when stressed Bonding in ceramics is more rigid and does not permit slip under stress The inability to slip makes it much more difficult for ceramics to absorb stresses
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Defects in Ceramics
Ceramics contain the same imperfections in their crystal structure as metals - vacancies, displaced atoms, interstitials, and microscopic cracks Internal flaws like cracks tend to concentrate stresses, especially tensile, bending, or impact
Hence, ceramics fail by brittle fracture much more readily than metals Strength is much less predictable due to random imperfections and processing variations
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Effect of Porosity
Porosity has a negative influence on elastic properties and strength
E = E0(1-1.9P+0.9P2) sfs = s0exp(-nP)

10 vol% porosity will decrease flexural strength by 50% from measured value of nonporous material.

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Concentration of Stress at Crack Tip

Adapted from Fig. 9.8(b), Callister & Rethwisch 3e.

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Ceramics in Compression
Defects that limit the tensile strength of ceramic materials are not as operative when compressive stresses are applied

Ceramics are substantially stronger in compression than in tension

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Strengthening of Ceramics
Make starting materials more uniform Decrease grain size in polycrystalline ceramic products Minimize porosity Introduce compressive surface stresses Use fiber reinforcement Heat treat
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Physical Properties of Ceramics

Density most ceramics are lighter than metals but heavier than polymers Melting temperatures - higher than for most metals
Some ceramics decompose rather than melt

Electrical and thermal conductivities - lower than for metals; but the range of values is greater, so some ceramics are insulators while others are conductors Thermal expansion less than metals, thermal shock due to brittleness.
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Oxides

SiO2

ZnO
YBa2Cu3O7

~ 10-20

~ 10-8 Semiconductors
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~ 103 (-cm)-1 Metals

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Insulators
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Adapted from Fig. 7.1 R. E. Hummel Electronic Properties of Materials, 1993

Guide to Processing Ceramics

Processing of ceramics can be divided into two basic categories:
1. Molten ceramics - major category of molten ceramics is glassworking (solidification processes) 2. Particulate ceramics - traditional and new ceramics (particulate processing)

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