Why do we care about crystal structures,

directions, planes ?
Physical properties of materials depend on the geometry of crystals

ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?
(for now, focus on metals)

• How does the density of a material depend on

its structure?

• When do material properties vary with the

sample (i.e., part) orientation?

Chapter 3- 1
 Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r

COOLING
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-
 MATERIALS AND PACKING
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.18(a),

LONG RANGE ORDER Callister 6e.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.18(b),
Callister 6e.

SHORT RANGE ORDER Chapter 3- 3

 Unit Cell Concept

• The unit cell is the smallest structural unit or building block that uniquely can
describe the crystal structure. Repetition of the unit cell generates the entire
crystal. By simple translation, it defines a lattice .

Lattice Parameter : Repeat distance

a in the unit cell, one for in each
dimension
b

Chapter 3-
 Crystal Systems

• Units cells and lattices in 3-D:

– When translated in each lattice parameter direction, MUST fill 3-D space
such that no gaps, empty spaces left.

c
b
Lattice Parameter : Repeat distance
a in the unit cell, one for in each
dimension

Chapter 3-
 Atomic stacking in 3-D

• Two types
• Stacking of atomic planes which are not closest packed
• Primitive or simple cubic and Body-centered cubic lattices
• Stacking of atomic planes which are closest packed
• Face-centered cubic and hexagonal close-packed lattices

Non-close arrangement of spheres Closest arrangement of spheres

Planar stacking in simple cubic and BCC lattices

Simple Cubic Body-Centered Cubic

Coordination number = 6 Coordination number = 8

 SIMPLE CUBIC STRUCTURE (SC)
• Rare due to poor packing (only Po has this structure)
• Close-packed directions are cube edges.
Closed packed direction is where • Coordination # = 6
the atoms touch each other (# nearest neighbors)

(Courtesy P.M. Anderson)

Chapter 3- 5
 ATOMIC PACKING FACTOR
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 (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. 3.19,
Callister 6e. Chapter 3- 6
BODY CENTERED CUBIC STRUCTURE
(BCC)
• Close packed directions are 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

2 atoms/unit cell: 1 center + 8 corners x 1/8

(Courtesy P.M. Anderson) Chapter 3- 7

 ATOMIC PACKING FACTOR: BCC
• APF for a body-centered cubic structure = 0.68
Close-packed directions:
length = 4R
= 3a
3a

R
a 2a
atoms volume
4
unit cell 2 ( 3a/4 ) 3
3 atom
APF =
volume
a3
unit cell
Chapter 3- 8
FCC and HCP lattices

HCP
FCC
Planar stacking in FCC crystals

Coordination number = 12
FACE CENTERED CUBIC STRUCTURE
(FCC)
• Close packed directions are 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 7e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

(Courtesy P.M. Anderson)

Chapter 3- 9
 ATOMIC PACKING FACTOR: FCC
• APF for a body-centered cubic structure = 0.74
Close-packed directions:
length = 4R
= 2a
Unit cell c ontains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
atoms volume
4
unit cell 4 ( 2a/4 ) 3
3 atom
APF =
volume
a3
unit cell
Chapter 3- 10
Planar stacking in HCP crystals

Coordination number = 12
 HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

B sites Middle layer

A sites Bottom layer

Adapted from Fig. 3.3,
Callister 6e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 Chapter 3- 12
 HCP lattice
- Unit cell volume -
 HCP lattice
- Height : Atomic Radius Relation -
 Atomic packing Factor of HCP lattice

Same as APF of FCC lattice !!!

Arrangement of unit cells in 3-D
Arrangement of unit cells in 3-D
All possible arrangements of unit cells in 3-D
 THEORETICAL DENSITY, 
# atoms/unit cell Atomic weight (g/mol)

 nA
Volume/unit cell Vc N A Avogadro's number
(cm 3 /unit cell) (6.023 x 10 23 atoms/mol)

Example: Copper
Data from Table inside front cover of Callister (see next slide):
• crystal structure = FCC: 4 atoms/unit cell
• atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
• atomic radius R = 0.128 nm (1 nm = 10 cm) -7

Vc = a 3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10 -23 cm 3

Result: theoretical Cu = 8.89 g/cm 3
Compare to actual: Cu = 8.94 g/cm 3
Chapter 3- 14
 Theoretical Density, 
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
a a = 4R/ 3 = 0.2887 nm

atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= actual = 7.19 g/cm3
a3 6.023 x 1023
volume atoms
unit cell mol Chapter 3 -
 Characteristics of Selected Elements at 20C
At. Weight Density Crystal Atomic radius
Element Symbol (amu) (g/cm 3 ) Structure (nm)
Aluminum Al 26.98 2.71 FCC 0.143
Argon Ar 39.95 ------ ------ ------
Barium Ba 137.33 3.5 BCC 0.217
Beryllium Be 9.012 1.85 HCP 0.114
Boron B 10.81 2.34 Rhomb ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ ------ teristics of
Cadmium Cd 112.41 8.65 HCP 0.149 Selected
Elements",
Calcium Ca 40.08 1.55 FCC 0.197 inside front
Carbon C 12.011 2.25 Hex 0.071 cover,
Callister 6e.
Cesium Cs 132.91 1.87 BCC 0.265
Chlorine Cl 35.45 ------ ------ ------
Chromium Cr 52.00 7.19 BCC 0.125
Cobalt Co 58.93 8.9 HCP 0.125
Copper Cu 63.55 8.94 FCC 0.128
Flourine F 19.00 ------ ------ ------
Gallium Ga 69.72 5.90 Ortho. 0.122
Germanium Ge 72.59 5.32 Dia. cubic 0.122
Gold Au 196.97 19.32 FCC 0.144
Helium He 4.003 ------ ------ ------
Hydrogen H 1.008 ------ ------ ------ Chapter 3- 15
 DENSITIES OF MATERIAL CLASSES
Graphite/
metals ceramic s polymer s Metals/
Alloys
Ceramics/ Polymers
Composites/
fibers
Semicond
Why? 30
Based on data in Table B1, Callister
Platinum
Metals have... 20 Gold, W
Tantalum
*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
• close-packing Epoxy composites (values based on
60% volume fraction of aligned fibers
(metallic bonding) 10 Silver, Mo
Cu,Ni
in an epoxy matrix).

• large atomic mass Steels

 (g/cm 3 )
Tin, Zinc
Zirconia
Ceramics have... 5
Titanium
4 Al oxide
• less dense packing Diamond
Si nitride
3
(covalent bonding) Aluminum Glass -soda
Concrete
Glass fibers
PTFE
• often lighter elements 2 Magnesium
Silicon
G raphite
GFRE*
Carbon fibers
Silicone CFRE *
Polymers have... PVC
PET
Aramid fibers
AFRE *
• poor packing 1 PC
HDPE, PS
PP, LDPE
(often amorphous)
• lighter elements (C,H,O) 0.5 Wood
Composites have... 0.4
0.3
• intermediate values Data from Table B1, Callister 6e.
Chapter 3- 16
 POLYMORPHISM & ALLOTROPY
• Some materials may exist in more than one crystal
structure, this is called polymorphism.
• If the material is an elemental solid, it is called allotropy.
An example of allotropy is carbon, which can exist as
diamond, graphite, and amorphous carbon.

Chapter 3-
 Boron Nitride Allotropy

Hexagonal (h-BN): Soft

Properties of BN
change with crystal
sp2 structure

Cubic (c-BN) : Exteremely Hard

sp3

Chapter 3-
 Fullerenes
B36N36 B12N12
B
4.3 Å N
C

C60

6.8 Å
7.2 Å

Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Family of Planes

Chapter 3-
Chapter 3-
Interplanar spacing

Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
 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

No. of diameters included

# atoms
a 2
LD   3.5 nm 1
length 2a

Chapter 3-
 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 7e. Radius of iron R = 0.1241 nm

atoms
No. of circles included
2D repeat unit 1
1 atoms atoms
Planar Density = = 2 = 12.1 = 1.2 x 10 19

area a2 4 3 nm 2
m2
R
2D repeat unit 3
Chapter 3-
 Planar Density of (111) Iron
Solution (cont):  (111) plane 1 atom in plane/ unit surface cell

Body centers
2a atoms in plane
atoms above plane

nit
atoms below plane

u
eat
ep
3
h a
r
2D 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
area 16 3 2
2
nm m2
R
2D repeat unit 3
Chapter 3-
HCP unit cell

Chapter 3-
 HCP unit cell

The hexagonal prism has three equivalent unit cells

Each unit cell contains 6/3 = 2 atoms (1/8 x 8 + 1)
Chapter 3-
 HCP unit cell
If we want to find out the total number of atoms in the hexagonal
Unit cell based upon the total number of atoms in each individual
Sub unit cell:
• There are a total of X = 3 sub unit cells
• In each of the top and bottom faces (F = 2) of the sub unit cell, only
• M = 1 of the outer Corner atoms is unshared 2 of the outer corner atoms are shared
• Hence, in the three faces of the three subunit cells in one hexagonal face,
there are a total of H = 3 unshared outer corner atoms
• The total contribution of each of the outer corner atom to each subunit cell
is G = 1/6.
• The interior corner atom of the subunit cell (with a contribution of
J = ½ to each hexagonal face) is shared equally by the three
Sub unit cells; so its contribution is Q = 1/3 for each sub unit cell
• Each subunit cell contains a total of T = 1 atom within its main body
• Hence the total number of atoms in the hexagonal unit cell is given by:

X [ F(MxG + JxQ) + T ] + (FxHxG) = 6

Chapter 3-
Chapter 3-
HCP Crystallographic Directions

Chapter 3-
HCP Crystallographic Directions

(u'v'w')

Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
 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. 3.8(a), Callister 7e.

Chapter 3-
Chapter 3-
Chapter 3-
 Solidification of Polycrystalline Materials
• A space lattice is formed by adding unit cells one after the other in three dimensions
• It is possible to produce a macroscopic visible piece of a metal, formed by repetition of unit cells of crystal structure of that metal
in three dimensions of 103 to 108 atomic diameters
• Such a piece is called a ‘single crystal’ of that metal
• Single crystals are quite common in naturally occurring minerals like galena, quartz, fluorite, etc.
• It is possible to grow such single crystals of metals in laboratory (the science of single crystal growth had become important since
the development of semi-conductors, transistors, lasers, etc.
• The crystal axes in a single crystal are in the same direction everywhere, i.e., atoms are oriented in one direction only
• There are no grains boundaries, the bounding surfaces are the only surfaces present
• A turbine blade of single crystal of titanium has proved a great success
• If a pure liquid metal is cooled very slowly, then at its freezing temperature, solidification begins

Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Solidification of Polycrystalline Materials

Chapter 3-
 Solidification of Polycrystalline Materials
• This process occurs in two stages:
– Nucleation
– Growth of nuclei

• Nucleation
– One small particle of crystalline solid first begins to form at a point within the liquid (under proper conditions)
– It is called nucleus (it is different than nucleus of an atom)
– It is a collection of many atoms, which is stable in the liquid
– As more and more atoms transfer themselves to this growing solid, it becomes macroscopically large
– This whole solid, thus formed is a single crystal

Chapter 3-
Solidification of Polycrystalline Materials

Chapter 3-
Solidification of Polycrystalline Materials

Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Dendritic solidification
As the molten pure metal cools below its freezing point,
crystallisation will begin.
It starts out with a single unit – (e.g. BCC for Tungsten).

New atoms will join the 'seed crystal' and grow onto the BCC Unit: Higgins Fig 4.3

structure much like a snowflake (except the metal is forming

in liquid, not a cloud of droplets).

The branched crystal Snowflake: Wikipedia

is called a 'dendrite‘
(Greek for tree).

Chapter 3-
 Dendrite of Silver: Wikipedia

Engineering Materials and Processes

Chapter 3-
Impurities
Above:
Dendritic formation of
grains.

Below:
Etched metal showing
dendritic structure with
porosity where molten
metal was not available
to fill the voids.

The jumbled, chaotic area between grains. The

irregular nature of the grain boundary is one source of
creep in metals but it is a barrier to dislocation
mobility. www.spaceflight.esa.int

Chapter 3-
Chapter 3-
Grain Boundaries

• In pure metals, dendrites

disappear once solidification is
complete
• If impurities were in the melt,
they may get left out of the
growing grain and end up at the
grain boundaries
• This is why a small amount of
impurity can destroy the
mechanical properties – causing
brittleness and cracks along the
crystal boundaries

Engineering Materials and Processes

Chapter 3-
Dendrites to Grains
Each dendrite forms independently, so the outer arms of neighbouring
dendrites make contact with each other at irregular angles and this
leads to the irregular overall shape of crystals.

Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
 Solidification of Real Crystals
• Dotted red line indicates solidification curve for a “pure” metal at (a) extremely slow cooling
rate, and (b) a constant pressure of 1 atm. It takes place by pure “planar growth”.
• Pure metals in reality neither solidify purely by dendritic growth nor by planar growth but a
combination of the two since neither of the above two conditions are fulfilled (solid black line)

(1)

(4)

(3)
(2)

Chapter 3-
 Solidification of Real Crystals
(1) A metal is heated above its melting point for complete melting since melting at the
theoretical melting temperature (Tm) will take a substantially larger amount of time and might
not take place at all due to atmospheric pressure much different than 1 atm or presence of
impurities or alloying elements
(2) When heating is stopped, temperature drops abruptly reaching a value below T m known as
undercooling. At this point, a numerous number of embryos suddenly form but hardly any
of them are stable
(3) Embryos reach a critical size and transform into nuclei. The nuclei now grow very slowly
into dendrites with needle-like arm edges since diffusion is very slow (T < T m). As
dendrites keep on growing, latent heat of fusion is continuously being rejected from the
dendrite-liquid interface into the solidification front. This gradually raises the temperature
of the surrounding liquid and the diffusion rate thus increases gradually. At the same time,
dendritic edges slowly broaden due to increasing diffusion rate and flatten out
progressively. As soon as the temperature reaches Tm, the mode of growth shifts from
dendritic to planar. However, growth rate from (3) to (4) has been quite retarded due to
lower cumulative diffusion rate
(4) Planar growth continues at Tm till the solidification is complete. However, it completes at a
time relatively later than the case if pure planar growth had taken place. The time lag is
shown in the figure. This explains why in real metallic materials, the solidification is not
complete till the onset of the solidus temperature since phase diagrams are constructed in
Chapter 3-
instruments which operate at extreme slow cooling rates and also maintain a constant
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Chapter 3-
Grains
A section through a cast aluminium ingot,
polished and etched in acid.

The crystals are all the same (pure

aluminium), but each crystal lattice is
randomly tilted and so reflects the light
differently. This is why they look bright or
dark.

Note a metal “grain” is not like the “grain”

in wood. It means crystal.

Grains in cast
aluminium
www.spaceflight.esa.int

Chapter 3-
Rapid solidification

By cooling fast enough, tiny

crystals are formed – or even
none at all. (glassy metal)
Any impurities dispersed in the
melt will remain so in the
amorphous solid.
The metal is more uniform in
composition, stronger and
tougher, but still malleable and
ductile.
But cooling so fast (a million
o
C per sec) means only very
thin bits have been made.
Amorphous (Glassy) Metals
http://metallurgyfordummies.com/amorphous-metal/

Chapter 3-
Chapter 3-
Chapter 3-
 SINGLE VS POLYCRYSTALS
• Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
E (diagonal) = 273 GPa
Data from Table 3.3,
Callister 6e.
(Source of data is R.W.
Hertzberg, Deformation
and Fracture Mechanics of
Engineering Materials, 3rd
ed., John Wiley and Sons,
1989.)
200 m Adapted from Fig. 4.12(b),
Callister 6e.
(Fig. 4.12(b) is courtesy of
L.C. Smith and C. Brady,
the National Bureau of
Standards, Washington,
DC [now the National
Institute of Standards and
Technology, Gaithersburg,
MD].)
Chapter 3- 19
 Anisotropy and Texture
• Different directions in a crystal have a different APF.

• For instance, atoms along the edge of FCC unit cell are more separated than
along the face diagonal. This causes anisotropy in the properties of crystals.

• For example, the deformation amount depends on the direction in which a

stress is applied, other properties are thermal conductivity, optical
properties, magnetic properties, hardness, etc.

• In some polycrystalline materials, grain orientations are random, hence bulk

material properties are isotropic, i.e. equivalent in each direction

• Some polycrystalline materials have grains with preferred orientations

(texture), so properties are dominated by those relevant to the texture
orientation and the material exhibits anisotropic properties.

Chapter 3-
 X-RAYS TO CONFIRM CRYSTAL STRUCTURE
• Incoming X-rays diffract from crystal planes.
de
te c
to

”
r

“1
i n ra y
s
co s
X-
y reflections must
r- a
m
be in phase to
in

”
X

“2
g
detect signal

“1
g

”
extra
oi
n 
“2
distance tg Adapted from Fig. 3.2W,
 u 
”
travelled o Callister 6e.
by wave “2” spacing
d between
planes

• Measurement of: x-ray

Critical angles, c, intensity d=n /2sin c
(from
for X-rays provide
detector)
atomic spacing, d.

c
Chapter 3- 20
 SCANNING TUNNELING
MICROSCOPY
• Atoms can be arranged and imaged
Photos produced from the
work of C.P. Lutz,
Zeppenfeld, and D.M.
Eigler. Reprinted with
permission from
International Business
Machines Corporation,
copyright 1995.

Carbon monoxide Iron atoms arranged on

molecules arranged on a a copper (111) surface.
platinum (111) surface. These Kanji characters
represent the word
“atom”.

Chapter 3- 21
 DEMO: HEATING AND
COOLING OF AN IRON WIRE
The same atoms can have
• Demonstrates "polymorphism" more than one crystal
structure.
Temperature, C
Liquid
1536
BCC Stable
1391
longer
heat up
FCC Stable
shorter!
914 longer!
BCC Stable
cool down
Tc 768 magnet falls off
shorter
Chapter 3- 22