STRUCTURES OF

METALS &
CERAMICS

By: Syed Khawar Hussain

Chapter 3 - 1
Chapter 3: Structures of Metals & Ceramics
ISSUES TO ADDRESS...
• What is the difference in atomic arrangement
between crystalline and noncrystalline solids?

• What features of a metal’s/ceramic’s atomic

structure determine its density?

• How do the crystal structures of ceramic

materials differ from those for metals?

• Under what circumstances does a material

property vary with the measurement direction?

Chapter 3 - 2
 Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.41(a),
Callister & Rethwisch 4e.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.41(b),
Callister & Rethwisch 4e.

Chapter 3 - 3
 Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have

lower energies.
Chapter 3 - 4
 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.
- Electron cloud shields cores from each other
• Metals have the simplest crystal structures.

We will examine three such structures...

Chapter 3 - 5
 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)

Click once on image to start animation

(Courtesy P.M. Anderson)

Chapter 3 - 6
 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
volume
atoms atom
a 4
unit cell 1 p (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.43,
Callister & Rethwisch 4e. Chapter 3 - 7
 Body Centered Cubic Structure (BCC)
• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

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

• Coordination # = 8

Adapted from Fig. 3.2,

Click once on image to start animation Callister & Rethwisch 4e.
(Courtesy P.M. Anderson)
2 atoms/unit cell: 1 center + 8 corners x 1/8
Chapter 3 - 8
 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
Adapted from R length = 4R = 3 a
Fig. 3.2(a), Callister &
Rethwisch 4e.
a
atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell Chapter 3 - 9
 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

Adapted from Fig. 3.1, Callister & Rethwisch 4e.

Click once on image to start animation
(Courtesy P.M. Anderson) 4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

Chapter 3 - 10
 Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2 a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister & atoms volume
Rethwisch 4e. 4
unit cell 4 p ( 2a/4) 3
3 atom
APF =
3 volume
a
unit cell
Chapter 3 - 11
 Theoretical Density, r

Mass of Atoms in Unit Cell

Density = r =
Total Volume of Unit Cell

nA
r =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.022 x 1023 atoms/mol

Chapter 3 - 12
 Theoretical Density, r
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
Adapted from
Fig. 3.2(a), Callister &
a a = 4R/ 3 = 0.2887 nm
Rethwisch 4e.
atoms
g
unit cell 2 52.00 rtheoretical = 7.18 g/cm3
mol
r= ractual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol Chapter 3 - 13
 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

Adapted from Fig. 2.7, Callister & Rethwisch 4e. (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.
Chapter 3 - 14
 Ceramic Crystal Structures
Oxide structures
– oxygen anions larger than metal cations
– close packed oxygen in a lattice (usually FCC)
– cations fit into interstitial sites among oxygen ions

Chapter 3 - 15
 Factors that Determine Crystal Structure
1. Relative sizes of ions – Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.
- - - - - -
+ + +
Adapted from Fig. 3.4,
Callister & Rethwisch 4e.
- - - - - -
unstable stable stable
2. Maintenance of
Charge Neutrality : F-
CaF 2 : Ca 2+ +
--Net charge in ceramic
cation anions
should be zero.
--Reflected in chemical F-
formula:
A m Xp
m, p values to achieve charge neutrality
Chapter 3 - 16
 Coordination Number and Ionic Radii
r cation
• Coordination Number increases with r
anion
To form a stable structure, how many anions can
surround around a cation?
r cation Coord. ZnS
r anion Number (zinc blende)
Adapted from Fig. 3.7,
< 0.155 2 linear Callister & Rethwisch 4e.

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)
Adapted from Fig. 3.5,
Callister & Rethwisch 4e.

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic Adapted from Fig. 3.6,
Adapted from Table 3.3, Callister & Rethwisch 4e.
Callister & Rethwisch 4e.
Chapter 3 - 17
 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) • Answer:
Al 3+ 0.053 rcation 0.077
=
Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069 = 0.550
Ca 2+ 0.100
based on this ratio,
-- coord # = 6 because
Anion
0.414 < 0.550 < 0.732
O2- 0.140
-- crystal structure is NaCl
Cl - 0.181
Data from Table 3.4,
F- 0.133 Callister & Rethwisch 4e.
Chapter 3 - 18
 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

Adapted from Fig. 3.5,

Callister & Rethwisch 4e.

Chapter 3 - 19
 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

Adapted from Fig. 3.5,

Callister & Rethwisch 4e.

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

Chapter 3 - 20
 AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende

Cesium Chloride structure:

rCs + 0.170
= = 0.939
rCl- 0.181

 Since 0.732 < 0.939 < 1.0,

cubic sites preferred

Adapted from Fig. 3.6,

So each Cs+ has 8 neighbor Cl-
Callister & Rethwisch 4e.

Chapter 3 - 21
 AX2 Crystal Structures
Fluorite structure

• Calcium Fluorite (CaF2)

• Cations in cubic sites

• UO2, ThO2, ZrO2, CeO2

• Antifluorite structure –
positions of cations and
anions reversed

Adapted from Fig. 3.8,

Callister & Rethwisch 4e.

Chapter 3 - 22
Density Computations for Ceramics

Number of formula units/unit cell

n¢(SAC + SAA )
r=
VC N A
Avogadro’s number
Volume of unit cell

SAC = sum of atomic weights of all cations in formula unit

SAA= sum of atomic weights of all anions in formula unit

Chapter 3 - 23
 Densities of Material Classes
In general Graphite/
rmetals > rceramics > rpolymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum
Based on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia

r (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
• less dense packing 3
Diamond
Si nitride
Aluminum Glass -soda
• often lighter elements Concrete
Silicon PTFE
Glass fibers
GFRE*
2 Carbon fibers
Polymers have... Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1 HDPE, PS
(often amorphous) PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• intermediate values 0.3

Data from Table B.1, Callister & Rethwisch, 4e.
Chapter 3 - 24
 Crystals as Building Blocks
• Some engineering applications require single crystals:
-- diamond single -- turbine blades
crystals for abrasives Fig. 9.40(c), Callister &
Rethwisch 4e. (Fig. 9.40(c)
(Courtesy Martin Deakins,
courtesy of Pratt and
GE Superabrasives,
Whitney).
Worthington, OH. Used with
permission.)

• Properties of crystalline materials

often related to crystal structure.
-- Ex: Quartz fractures more easily
along some crystal planes than
others.
(Courtesy P.M. Anderson)

Chapter 3 - 25
 Polycrystals Anisotropic
• Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
1 mm

• Nb-Hf-W plate with an electron beam weld. Isotropic

• Each "grain" is a single crystal.
• If grains are randomly oriented,
overall component properties are not directional.
• Grain sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
Chapter 3 - 26
 Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa
Data from Table 3.7,
-Properties vary with Callister & Rethwisch
4e. (Source of data is
direction: anisotropic. R.W. Hertzberg,
Deformation and
-Example: the modulus Fracture Mechanics of
Engineering Materials,
of elasticity (E) in BCC iron: 3rd ed., John Wiley and
Sons, 1989.)
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not 200 mm Adapted from Fig.
5.19(b), Callister &
vary with direction. Rethwisch 4e.
(Fig. 5.19(b) is courtesy
-If grains are randomly of L.C. Smith and C.
Brady, the National
oriented: isotropic. Bureau of Standards,
Washington, DC [now
(Epoly iron = 210 GPa) the National Institute of
Standards and
-If grains are textured, Technology,
anisotropic. Gaithersburg, MD].)

Chapter 3 - 27
 Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
Iron
liquid
1538ºC
carbon
BCC -Fe
diamond, graphite
1394ºC
FCC -Fe
912ºC
BCC -Fe

Chapter 3 - 28
 Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.

7 crystal systems

14 crystal lattices

a, b, and c are the lattice constants

Fig. 3.20, Callister & Rethwisch 4e.

Chapter 3 - 29
 Point Coordinates
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2 ½½½

000
y
a b
Point coordinates for unit cell
x · corner are 111
z 2c
·
Translation: integer multiple of
· · lattice constants  identical
b y position in another unit cell
b
Chapter 3 - 30
 Crystallographic Directions
z Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

x [uvw]

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a
negative index
families of directions <uvw>
Chapter 3 - 31
 Linear Density
Number of atoms
• Linear Density of Atoms  LD =
Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

# atoms
a 2
LD = = 3.5 nm-1
Adapted from
Fig. 3.1(a),
length 2a
Callister &
Rethwisch 4e.

Chapter 3 - 32
 Drawing HCP Crystallographic Directions (i)

Algorithm (Miller-Bravais coordinates)

1. Remove brackets
2. Divide by largest integer so all values
are ≤ 1
3. Multiply terms by appropriate unit cell
dimension a (for a1, a2, and a3 axes)
or c (for z-axis) to produce
projections
4. Construct vector by stepping off
these projections

Adapted from Figure 3.25,

Callister & Rethwisch 4e.

Chapter 3 - 33
 Drawing HCP Crystallographic Directions (ii)
• Draw the [1 2 13] direction in a hexagonal unit cell.
Adapted from p. 62, Algorithm a1 a2 a3 z
Callister &
Rethwisch 8e. 1. Remove brackets -1 -2 1 3
1 2 1
[1213] 2. Divide by 3 - - 1
s 3 3 3
3. Projections

4. Construct Vector
start at point o
proceed –a/3 units along a1 axis to point p
p –2a/3 units parallel to a2 axis to point q
r q a/3 units parallel to a3 axis to point r
c units parallel to z axis to point s

[1213] direction represented by vector from point o to point s

Chapter 3 - 34
Determination of HCP Crystallographic Directions (ii)

Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of three-
axis (a1, a2, and z) unit cell dimensions
a and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas,
for three-axis coordinates
5. Convert to four-axis Miller-Bravais lattice
coordinates using equations below:
1 1
Adapted from p. 74, Callister & u= (2u¢ - v ¢) v = (2v ¢ - u¢)
Rethwisch 4e. 3 3
t = -(u +v) w = w¢
6. Adjust to smallest integer values and
enclose in brackets [uvtw] Chapter 3 - 35
 Determination of HCP Crystallographic Directions (ii)
Adapted
from p. 74, Determine indices for green vector
Callister &
Rethwisch Example a1 a2 z
4e.
1. Reposition not needed
2. Projections a a 0c
1 1 0
3. Reduction 1 1 0
4. Brackets [110]
5.
Convert to 4-axis parameters
1 1 1 1
u = [(2)(1) - (1)] = v = [(2)(1) - (1)] =
3 3 3 3
1 1 2
t = -( + ) = - w =0
3 3 3
6. Reduction & Brackets

1/3, 1/3, -2/3, 0 => 1, 1, -2, 0 => [ 1120 ]

Chapter 3 - 36
 Crystallographic Planes

Adapted from Fig. 3.26,

Callister & Rethwisch 4e.
Chapter 3 - 37
 Crystallographic Planes
• Miller Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of fractions &
common multiples. All parallel planes have
same Miller indices.

• Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)

Chapter 3 - 38
 Crystallographic Planes
z
example a b c
1. Intercepts 1 1  c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
Chapter 3 - 39
 Crystallographic Planes
z
example a b c c
1. Intercepts 1/2 1 3/4 ·
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 · y
·
3. Reduction 6 3 4 a b

4. Miller Indices (634) x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)

Chapter 3 - 40
 Crystallographic Planes (HCP)
• In hexagonal unit cells the same idea is used
z

example a1 a2 a3 c
1. Intercepts 1  -1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1 a2

3. Reduction 1 0 -1 1
a3

4. Miller-Bravais Indices (1011) a1

Adapted from Fig. 3.24(b),

Callister & Rethwisch 4e.

Chapter 3 - 41
 Crystallographic Planes
• We want to examine the atomic packing of
crystallographic planes
• Iron foil can be used as a catalyst. The
atomic packing of the exposed planes is
important.
a) Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these
planes.

Chapter 3 - 42
 Planar Density of (100) Iron
Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100) 4 3
a= R
3

Adapted from Fig. 3.2(c), Callister & Rethwisch 4e. Radius of iron R = 0.1241 nm
atoms
2D repeat unit 1
1 atoms atoms
19
Planar Density = = 2 = 12.1 = 1.2 x 10
area a2 4 3 nm 2 m2
R
2D repeat unit 3
Chapter 3 - 43
 Planar Density of (111) Iron
Solution (cont): (111) plane 1 atom in plane/ unit surface cell

2a atoms in plane
atoms above plane
atoms below plane

3
h= a
2
2
 4 3  16 3 2
area = 2 ah = 3 a = 3 
2
R÷
÷ = R
atoms  3  3
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
nm 2 m2
area 16 3 2
R
2D repeat unit 3
Chapter 3 - 44
 X-Ray Diffraction

• Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.
• Can’t resolve spacings  
• Spacing is the distance between parallel planes of
atoms.
Chapter 3 - 45
 X-Rays to Determine Crystal Structure
• Incoming X-rays diffract from crystal planes.

reflections must
be in phase for
a detectable signal
extra  Adapted from Fig. 3.38,
q q
distance
Callister & Rethwisch 4e.
travelled
by wave “2” spacing
d between
planes

Measurement of X-ray
n
critical angle, qc, intensity d=
(from 2 sin qc
allows computation of
detector)
planar spacing, d.
q
qc
Chapter 3 - 46
 X-Ray Diffraction Pattern
z z z
c c c

y (110) y y
a b a b a b
Intensity (relative)

x x x (211)

(200)

Diffraction angle 2q

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.40, Callister 4e.

Chapter 3 - 47
 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.
• Crystallographic points, directions and planes are specified in
terms of indexing schemes. Crystallographic directions and
planes are related to atomic linear densities and planar densities.

Chapter 3 - 48
 SUMMARY

• Materials can be single crystals or polycrystalline.

Material properties generally vary with single crystal
orientation (i.e., they are anisotropic), but are generally
non-directional (i.e., they are isotropic) in polycrystals
with randomly oriented grains.
• Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).
• X-ray diffraction is used for crystal structure and
interplanar spacing determinations.

Chapter 3 - 49
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 3 - 50