Crystal Structure

Metals-Ceramics

Ashraf Bastawros

www.public.iastate.edu\~bastaw\courses\Mate271.html

Material Sciences and Engineering

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Ceramic Crystal Structures

- Broader range of chemical composition than metals

with more complicated structures
- Contains at least 2 and often 3 or more atoms.
- Usually compounds between metallic ions (e.g. Fe,
Ni, Al) - called cations - and non-metallic ions (e.g.
O, N, Cl) - called anions
- Bonding will usually have some covalent character but
is usually mostly ionic

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 Ceramic Crystal Structure

o Still based on 14 Bravais lattices

o Cation: Metal, positively charged, usually
smaller
o Anion: Usually O, C, or N, negative charge,
usually larger.

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How do Cations and Anions arrange

themselves in space???
• Structure is determined by two characteristics:
1. Electrical charge
- Crystal (unit cell) must remain electrically
neutral
- Sum of cation and anion charges in cell is 0

2. Relative size of the ions

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 Ceramic Crystal Structures

- The ratio of ionic radii (rcation /r anion ) dictates

the coordination number of anions around each
cation.
- As the ratio gets larger (i.e. as rcation /r anion 1)
the coordination number gets larger and larger.

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Where do Cations and Anions fit ?

CN Radius Ratio Geometry

3 0.155 - 0.225 Triangular

4 0.255 - 0.414 Tetrahedron

6 0.414-0.732 Octahedron

8 0.732 - 1 Cube Center

rcation /r anion
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 Interstitial sites (Octahedral)

FCC
BCC

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Interstitial sites (Tetrahedral)

BCC FCC

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 Interstitial sites

-Any close packed array of N atoms contains

N octahedral interstitial sites
2N tetrahedral sites
- Octahedral sites are larger than tetrahedral sites

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Some common ceramic structures

Structure Lattice Ch. formula

Cesium Chloride (CsCl) SC MX

Rock salt (NaCl) FCC MX

Fluorite (CaF2) FCC MX2

Silicates (complex) (SiO2) FCC MX2

Corundum (Al2O3) hexagonal M2X3

Perovskite (CaTiO3) SC M’M’’X3

Spinel (MgAlO4 ) FCC M’M’’ X4

Diamond FCC

Graphite hexagonal
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 Note: What defines a lattice point

No of lattice (basis) points/unit cell

SC=1 BCC=2 FCC=4

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Cesium Chloride (CsCl)

Lattice: SC
Chemical formula: MX

- Atoms per lattice point =

- Formula units/unit cell =

Cs located on cube center

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 Differences between CsCl (SC) and Cr (BCC)

Cs
Cr
Cl

CsCl (SC) Cr (BCC)

No lattice point/unit cell one: (0,0,0) two: (0,0,0),
(0.5,0.5,0.5)
No atoms/lattice point two: (0,0,0), One/lattice pt.
(0.5,0.5,0.5)

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Rock Salt Structure (NaCl)

Lattice: FCC
Chemical formula: MX

- Atoms per lattice point =

- Formula units/unit cell =

MgO, FeO, NiO, CaO also

have rock salt structure

Na located on octahedral sites

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 Flourite Structure (CaF2 )
¼ distance of body diagonal

Ca2+
_
F

Lattice: FCC
Chemical formula: MX2 _
Ion/ Unit Cell: 4 Ca2++ 8 F = 12
Typical Ceramics: UO2 , ThO2 , and TeO2

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Corundum Structure (Al2O3)

Lattice: hexagonal
Chemical formula: M2X3 _
Ion/ Unit Cell: 12 Al3++ 18 O2
= 30
Typical Ceramics:
Al2O3 , Cr2O3 , α Fe2O3

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 Perovskite Structure (BaTiO3 , Ca TiO3)

Lattice: SC
Chemical formula: M’ M’’ X3
Atoms per lattice point = Ferroelectric
Piezoelectric
Ion/ Unit Cell =

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Diamond Cubic Structure

¬ All atoms are C

¬ 4 interior C atoms
(tetrahedrally coordinated with
corner and face-centered C
atoms)

¬ Covalent bonds (extremely strong)

¬ HARD
¬ Low electrical conductivity
¬ Optically transparent

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 Diamond Thin Film

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Carbon - Graphite

not
hcp

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 Fullerenes

Buckyball
C60

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Glass Structure
¬ The basic structural unit of a silicate glass is
the SiO4 tetrahedron
¬ Link together sharing corners to form a 3-D
network

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 Glass Structure
¬ Beyond the short range order the structure is random
¬ Other ions may also be present

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Polymorphism and Allotropy

¬ Some materials may have more than one crystal

structure depending on temperature and pressure - called
POLYMORPHISM
¬ Carbon (diamond, graphite, fullerenes)
¬ Silica (quartz, tridymite, cristobalite, etc.)
¬ Iron (ferrite, austenite)

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 Polymer Structures

¬ Chainlike structures of long polymeric molecules

(usually involving C, H, and O + other elements)
¬ Usually mostly noncrystalline
– Extremely complex and elongated molecules do not
readily “line up” on cooling to crystallize
¬ Structure is very dependent on thermal history
(so are properties)

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Atomic Densities
- Why do we care?
- Properties, in general, depend on linear and planar
density.

- Examples:
- Speed of sound along directions
- Slip (deformation in metals) depends on linear & planar
density
- Slip occurs on planes that have the greatest density
of atoms in direction with highest density
(we would say along closest packed directions on the closest packed
planes)
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 Linear and Planar Densities

Linear Densities
fraction of line length in a particular direction
that passes through atom centers

Planar Densities
fraction of total crystallographic plane area that
is occupied by atoms (plane must pass
through center of atom)

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Calculate the Linear Density

o Calculate the linear density of the (100)
direction for the FCC crystal

LD = LC/LL linear
density
LC = 2R circle length
LL = a line length

For FCC a = 2R√2

LD = 2R/(2R√2) = 0.71

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 Calculate the Planar Density
o Calculate the planar density of the (110)
plane for the FCC crystal

C A B C
B
A
D E F

F
E • Compute planar area
• Compute total “circle” area
D

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Semiconductor Structures

¬ Technologically, single crystals are very important

¬ More “perfect” than any other class of materials
(purer, fewer dislocations)
¬ Elemental semiconductors (Si and Ge) are of the
diamond cubic structure
¬ Compound semiconductors (GaAs, CdS) have
zincblende (similar to diamond cubic)

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 Reading Assignment

Shackelford 2001(5th Ed)

– Read Chapter 3, pp 59-64
Read ahead to page 88, 101-110
Check class web site:

www.public.iastate.edu\~bastaw\courses\Mate271.html 2

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