Ceramic Materials: Structures

Structures of ceramics •  Ionic crystals

•  Packing of atoms –  predominantly ionic bonding
–  periodic: crystals - e.g. fcc, bcc, –  ions
hcp •  cation: positively charged
cations are
–  random: glasses (amorphous) •  anion: negatively charged
usually
•  Complication for ceramics smaller than –  e.g. Mg is cation and O
anions is anion in MgO
–  often involving two or more •  treated as hard spheres
types of elements: e.g. Al2O3,
–  effects of sizes and charges of
MgAl2O4 ions on structure
–  bonding: a mixture of covalent –  rules guiding the structure
and ionic, e.g. SiC: 88% •  #1: cation be surrounded
covalent, 12% ionic; MgO: 73% by the maximum number of
ionic, 27% covalent anions possible, i.e. be
•  ionic: electrical neutrality shielded as much as
•  covalent: directionality possible from other
cations, and be in contact
–  ions (atoms) having different with each surrounding
sizes anions
Reading: 13.2-13.4 (5th ed), 12.2-12.4 (6th/7th ed)
MCEN90014: Materials Dr. K. Xia 1

Ceramic Materials: Structures

Coordination number (CN): the number of

nearest (touching) neighbouring ions

Therefore, for a certain cation-to-anion radius most likely CN

ratio (rC/rA), there is a preferred coordination for ceramics
number. For example, when the ratio is 0.3, the
coordination number can be 2, 3 or 4 in order to
satisfy the "in contact" rule. A coordination
number of 4 will be taken as that is the
maximum possible.
rC/rA determines the preferred CN
Caution: rC and rA changes slightly with CN HW: Follow example 12.1
to calculate rC/rA for CN of
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 Ceramic Materials: Structures
•  #2: bond strength of cation must be equal to that of anion to keep
local electrical neutrality [bond strength = valence (number of valence
electrons) of ion divided by CN], i.e.
valence of cation valence of anion
=
CN of cation CN of anion

–  Example
€ Mg ion in MgO has an coordination number of 6. What is the
coordination number for O?
Solution: valence of Mg = +2; valence of O = –2
+2 −2
=
6 CN of O

Thus, CN of O is 6.
€
+2/6 –2/6
Mg +2 –2 O
local neutrality

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Example
•  Table 12.3 (in 6th ed and table Solution
13.3 in 5th ed) gives the ionic radii The cation radius to anion radius ratio is
for K+ and O2- as 0.138 and 0.140 rc/ra = 0.138/0.140 = 0.986
nm, respectively. What would be Thus, CN = 8 for the cation, K.
the coordination number for each
O2- ion? Briefly describe the Bond strength balance
resulting crystal structure for K2O.
Explain why this is called the Valencecation Valenceanion
=
antifluorite structure. CNcation CN anion
+1 −2
=
8 CN anion
So, the rules of thumb may not work!
In this case, K cannot have a CN of 8 Thus, CNO = 16 ???
as that would require a CN of 16 for O
which is impossible geometrically. €
The next option would be for CNK = 4 This is impossible. In fact, K2O takes the
and CNO = 8 since the CN number for antifluorite structure with CNanion = 8 and
O has to double that for K to balance CNcation = 4.
the bond strength. This is allowed as The CN listed in the table is actually the maximum
K is bigger than the minimum size which will be taken if allowed. Otherwise, a smaller
required for a CN of 4. CN may be taken without causing instability.

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 Ceramic Materials: Structures
•  Interstices = Interstitial sites between ions: important in describing structures
–  Interstices in close packed structures (FCC and HCP)
•  tetrahedral: the space between one corner ion and 3 closest face-centre ions
–  CN=4
–  there are 8 tetrahedral sites in a fcc unit cell
–  there are 4 lattice sites in a fcc unit cell
–  ratio of number of tetrahedral interstitial sites to that of lattice sites = 2

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Ceramic Materials: Structures

•  Octahedral: the space between the 6 face-centre ions
–  CN=6
–  there are 4 equivalent octahedral sites in a fcc unit cell
–  there are 4 lattice sites in a fcc unit cell
–  ratio of number of octahedral interstitial sites to that of lattice sites = 1

This interstitial site is shared

by 4 neighbouring unit cells,
and thus only counted as 1/4.

For HCP based structures, the interstitial structures are exactly the same.
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 Ceramic Materials: Structures

The octahedral site is formed by 3 bottom

layer ions (yellow) and 3 top layer ions (red)

The tetrahedral site is formed by 1 bottom

layer ions (yellow) and 3 top layer ions (red)

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Ceramic Materials: Structures

Typical structures
•  Description
–  Anions fill lattice sites to
form the basic structure
–  Cations fill interstitial
sites
•  Typical structures with
anions forming FCC
–  1. Rock salt structure (=
NaCl structure)
•  Formula = AX
•  e.g. NaCl, MgO
•  Anions = FCC
•  Cations = fill all of the
octahedral sites
•  CN = 6 for both
anions and cations

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 Ceramic Materials: Structures
–  2. Zinc blende structure
•  Formula = AX
•  e. g. ZnS, β-SiC
•  Anions = FCC
•  Cations = fill half of
the tetrahedral sites
•  CN = 4 for both
anions and cations

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Ceramic Materials: Structures

–  3. Antifluorite structure
•  Formula = A2X
•  e. g. Li2O, Na2O
•  Anions = FCC
•  Cations = fill all of the tetrahedral sites
•  CN = 8 for anions and 4 for cations

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 Ceramic Materials: Structures
–  4. Spinel structure
Mg Al O
•  Formula =
AB2X4
•  e. g. MgAl2O4
•  Anions = FCC
•  Cations A = fill
1/8 of the
tetrahedral
sites
•  Cations B = fill
half of the
octahedral sites
•  CN = 4 for
cation A, 6 for
cation B and 4
for anion

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Ceramic Materials: Structures

•  Typical structures with
anions forming simple cubic
–  5. Cesium chloride
structure
•  Formula = AX
•  e. g. CsCl, CsBr
•  Anions = simple cubic
•  Cations = fill all of the
cubic centres
•  CN = 8 for both
anions and cations

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 Ceramic Materials: Structures
–  6. Fluorite structure
•  Formula = AX2
•  e. g. CaF2, ZrO2
(> 2370°C)
•  Anions = simple cubic
•  Cations = fill half of
the cubic centres
•  CN = 4 for anions and
8 for cations

An alternative way of describing

this structure:
Cations = FCC
Anions = fill all the tetrahedral
sites
(This is exactly the opposite to
that of the antifluorite structure!)

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Ceramic Materials: Structures

•  Typical structures with –  8. Wurtzite structure
anions forming HCP •  Formula = AX
–  7. Corundum structure •  e. g. AlN, α-SiC
•  Formula = A2X3 •  Anions = HCP
•  e. g. α-Al2O3, Fe2O3 •  Cations = fill half of
•  Anions = HCP the tetrahedral sites
•  Cations = fill 2/3 of •  CN = 4 for both
the octahedral sites cations and anions
•  CN = 4 for anions and
6 for cations

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 Ceramic Materials: Structures
•  Other structures
–  9. Perovskite structure
•  Formula = ABX3
•  e. g. CaTiO3, BaTiO3
•  A at corners, B at
body centre, anions
at face centres
•  CN of A = 12, CN of
B = 6, CN of anion =
6

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Ceramic Materials: Structures

–  10. Silicon dioxide (SiO2)
•  Basic unit = SiO4
tetrahedron
•  Three crystalline forms
–  quartz = hexagonal
–  tridymite = monoclinic
–  cristobalite = cubic
(diamond like)
•  Silica glass: random
arrangement of the SiO4
tetrahedrons

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 Ceramic Materials: Structures
–  11. Diamond (C) –  12. Graphite (C)
•  Variant of the zinc blende •  Simple hexagonal structure
structure (C occupies both
Zn and S sites)

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Ceramic Materials: Structures

–  13. Fullerene (C) –  14. C
•  molecule consisting of 60 nanotube
carbon atoms (C60) •  graphite
•  molecules form FCC solid sheet
rolled into
tube
20 hexagons 12 pentagons capped by
half
buckyballs
at the ends

Very strong and stiff

TS = 50-200 GPa
E = 1000 GPa
< 100 nm

buckyball
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 Ceramic Materials: Structures
–  15. Graphene (C)
•  two dimensional

20 hexagons

buckyball
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