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Rick Holt
Queen’s University
KINGSTON, ONTARIO, CANADA.
Structures of Ceramics
• Bonding
• Crystal structures
• Point Defects
1
RH80
Ceramic Bonding
• Bonding:
-- Mostly ionic, some covalent.
-- % ionic character increases with difference in
electronegativity.
• Large vs small ionic bond character:
CaF2: large
SiC: small
Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition,
Copyright 1939 and 1940, 3rd edition. Copyright 1960 by
Cornell University.
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Slide 3
RH80 ceramics typically contain two or more elements in a stoichiometric combination (eg. CaF2, SiO2), which
means that crystalline ceramics can have very complex crystal structures – furthermore, the
inter-atomic bonding in a ceramic can vary from purely ionic to totally covalent, depending upon the
electronegativities of the atoms involved
Richard Holt, 11/1/2007
Ceramic Crystal Structures
Crystal Structures
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Site Selection
Which sites will cations occupy?
1. Size of sites
– does the cation fit in the site
– Are the cations/anion distances minimized
2. Stoichiometry
– if all of one type of site is full the remainder
have to go into other types of sites.
• Charge Neutrality: F-
--Net charge in the
CaF 2 : Ca 2+ +
structure must cation anions
be zero. F-
--General form: A m Xp
m, p determined by charge neutrality
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Cation Site Size
• Determine minimum rcation/ranion for OH site
(C.N. = 6)
2ranion + 2rcation = 2a
a = 2ranion
rcation
= 0 . 414
r anion
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NaCL (Rock Salt) Structure
Example: NaCl (rock salt) structure
rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
O2- rO = 0.140 nm
rMg/rO = 0.514
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AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende
Cesium Chloride structure:
rCs + 0 . 170
= = 0 . 939
rCl − 0 . 181
Site Selection
2. Stoichiometry
– If all of one type of site is full the remainder have
to go into other types of sites.
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AX2 Crystal Structures
Fluorite structure
• Perovskite
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RH81
Silicate Ceramics
Most common elements on earth are Si & O
– rSi = 0.04
– rO = -.14
– rSi/rO = 0.286 → cations prefer TD
Si4+
O2-
Amorphous Silica
• Silica gels - amorphous SiO2
– Si4+ and O2- not in well-ordered lattice
– Charge balanced by H+ (to form
OH-) at “dangling” bonds
• very high surface area > 200 m2/g
– SiO2 is quite stable, therefore unreactive
• makes good catalyst support
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Slide 17
RH81 another common class of ceramics is the family of silicate ceramics, composed primarily of silicon and
oxygen – given that Si and O are the two most abundant elements in the earth’s crust, the majority of
soils, rocks, clays, and sand can be classified as silicates – silicon dioxide (SiO2), also called silica, is the
simplest silicate – as is the case with many ceramic materials, silica has three polymorphic crystalline
forms: quartz, cristabolite, and tridymite
Most crystalline ceramics contain very complex 3-D arrangements, such as the cristobalite unit cell
shown here.
Richard Holt, 11/1/2007
Silica Glass
• Dense form of amorphous silica
– Charge imbalance corrected with “counter
cations” such as Na+
– Borosilicate glass is the pyrex glass used in
labs
• better temperature stability & less brittle than sodium
glass
Frenkel
Defect
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Impurities
• Impurities must also satisfy charge balance = Electroneutrality
• Ex: NaCl Na + Cl -
cation
• Substitutional cation impurity vacancy
Ca 2+
Na +
Na +
Ca 2+
initial geometry Ca 2+ impurity resulting geometry
Cl - Cl -
initial geometry O 2- impurity resulting geometry
Diffusion
• Because of the point defect structures than
must have a charge balance diffusion is
more complicated in ceramics that in metals
• e.g., the two vacant cites of a Shottky defect
must stay close together
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Ceramic Phase Diagrams
often part of a three component system such as Mg-Al-O can be treated as a
two component system if two ceramics are taken as end points
MgO-Al2O3 diagram:
Summary
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