Chapter 3:

Structures of Metals & Ceramics

Structures
The properties of some materials are
directly related to their crystal
structures.
Significant property differences exist
between crystalline and noncrystalline
materials having the same composition.

Energy and Packing

Non dense, random packing

Energy
typical neighbor
bond length

typical neighbor
bond energy

Dense, ordered packing

r
Energy
typical neighbor
bond length

typical neighbor
bond energy

Dense, ordered packed structures tend to have lower energies.

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Materials and Packing

Crystalline materials...
atoms pack in periodic, 3D arrays
typical of: -metals
-many ceramics
-some polymers

Noncrystalline materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline

crystalline SiO2

Si

Oxygen

noncrystalline SiO2
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Metallic Crystal Structures

How can we stack metal atoms to minimize
empty space?
2-dimensions

vs.

Metallic Crystal Structures

Tend to be densely packed.
Reasons for dense packing:
-Typically, only one element is present, so all
atomic radii are the same.
-- Metallic bonding is not directional.
-- Nearest neighbor distances tend to be small in
order to lower bond energy.
- The electron cloud shields cores from each
other
They have the simplest crystal structures.
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Simple Cubic Structure (SC)

Rare due to low packing density (only Po has this structure)
Close-packed directions are cube edges.
Coordination # = 6
(# nearest neighbors)

Atomic Packing Factor (APF)

Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
APF for a simple cubic structure = 0.52
atoms
unit cell

a
R=0.5a
close-packed directions
contains 8 x 1/8 =
1 atom/unit cell

APF =

volume
atom
4
(0.5a) 3
1
3
a3

volume
unit cell
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Body Centered Cubic Structure (BCC)

Atoms touch each other along cube diagonals.
All atoms are identical.

ex: Cr, W, Fe (), Tantalum, Molybdenum

Coordination # = 8
2 atoms/unit cell: 1 center + 8 corners x 1/8
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Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68
3a

a
2a

Close-packed directions:
length = 4R = 3 a

atoms
volume
4
( 3a/4) 3
2
unit cell
atom
3
APF =
volume
a3
unit cell

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Face Centered Cubic Structure (FCC)

Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

Coordination # = 12
4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8
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Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74
maximum achievable APF

2a

Close-packed directions:
length = 4R = 2 a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
atoms
volume
4
3
( 2a/4)
4
unit cell
atom
3
APF =
volume
3
a
unit cell
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Hexagonal Close-Packed Structure

(HCP another view)

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Hexagonal Close-Packed Structure

(HCP)
ABAB... Stacking Sequence
3D Projection

2D Projection
A sites

Top layer

B sites

Middle layer

A sites

Bottom layer

Coordination # = 12
APF = 0.74
c/a = 1.633

6 atoms/unit cell
ex: Cd, Mg, Ti, Zn
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ABAB... Stacking Sequence

X-Ray Diffraction

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X-Ray Diffractometer
Detector
Xray-Tube

Xray-Tube

le
p
m
a
s

Sample
Metal Target
(Cu or Co)
Detector

Braggs Equation
d = /2 sin

d distance between the

same atomic planes
monochromatic
wavelength
angle of diffractometer

Theoretical Density,
Density = =
=

where

Mass of Atoms in Unit Cell

Total Volume of Unit Cell

nA
VC NA

n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.022 x 1023 atoms/mol
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Theoretical Density,
Ex: Cr (BCC)
A (atomic weight) = 52.00 g/mol
n = 2 atoms/unit cell
R = 0.125 nm
R
atoms
unit cell

=
volume
unit cell

a
2 52.00

a3 6.022 x 1023

a = 4R/ 3 = 0.2887 nm
g
mol

theoretical

= 7.18 g/cm3

actual

= 7.19 g/cm3

atoms
mol

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Factors that Determine Crystal Structure

1. Relative sizes of ions Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.

unstable
2. Maintenance of
Charge Neutrality:

stable

--Net charge in ceramic

should be zero.
--Reflected in chemical
formula:

CaF 2 :

stable
Ca 2+ +
cation

Fanions
F-

A m Xp
m, p values to achieve charge neutrality
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Atomic Bonding in Ceramics

Bonding:
-- Can be ionic and/or covalent in character.
-- % ionic character increases with difference in
electronegativity of atoms.

Degree of ionic character may be large or small:

CaF2: large
SiC: small

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Coordination # and Ionic Radii

r cation
Coordination # increases with r
anion

To form a stable structure, how many anions can

surround a cation?
r cation
r anion
< 0.155

Coord
#
2
linear

0.155 - 0.225

0.225 - 0.414

4 tetrahedral

0.414 - 0.732

6 octahedral

0.732 - 1.0

triangular

cubic

ZnS
(zinc blende)

NaCl
(sodium
chloride)
CsCl
(cesium
chloride)
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Computation of Minimum Cation-Anion

Radius Ratio
Determine minimum rcation/ranion for an octahedral site

2ranion 2rcation 2a
a 2ranion

(C.N. = 6)

Measure the radii (blue

and yellow spheres)

Substitute for a in the

above equation

2ranion 2rcation 2 2ranion

ranion rcation 2ranion

rcation ( 2 1)ranion

rcation
2 1 0.414
ranion
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Example Problem: Predicting the Crystal

Structure of FeO
On the basis of ionic radii, what crystal structure would you
predict for FeO?
Cation Ionic radius (nm)
Al 3+
0.053
Fe 2+
0.077
Fe 3+
0.069
Ca 2+
0.100
Anion
O2Cl F-

0.140
0.181
0.133

Answer:

rcation 0.077

ranion 0.140
0.550
based on this ratio,
-- coord # = 6 because
0.414 < 0.550 < 0.732
-- crystal structure is similar to NaCl
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Rock Salt Structure

Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt) structure
rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
cations (Na+) prefer octahedral sites

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MgO and FeO

MgO and FeO also have the NaCl structure
O2-

rO = 0.140 nm

Mg2+

rMg = 0.072 nm

rMg/rO = 0.514
cations prefer octahedral sites

So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms

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AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende
Cesium Chloride structure:

rCs
rCl

0.170
0.939
0.181

Since 0.732 < 0.939 < 1.0,

cubic sites preferred
So each Cs+ has 8 neighbor Cl30

AX2 Crystal Structures

Fluorite structure
Calcium Fluorite (CaF2)
Cations in cubic sites
UO2, ThO2, ZrO2, CeO2
Antifluorite structure
positions of cations and
anions reversed

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ABX3 Crystal Structures

Perovskite structure
Ex: complex oxide
BaTiO3

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SUMMARY
Atoms may assemble into crystalline or amorphous structures.
Common metallic crystal structures are FCC, BCC and HCP.
Coordination number and atomic packing factor are the same
for both FCC and HCP crystal structures.
We can predict the density of a material, provided we know the
atomic weight, atomic radius, and crystal geometry (e.g., FCC,
BCC, HCP).
Interatomic bonding in ceramics is ionic and/or covalent.
Ceramic crystal structures are based on:
-- maintaining charge neutrality
-- cation-anion radii ratios.

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