Crystallography and

Structure

Overview:

Crystal Structure matter assumes a periodic

shape
Non-Crystalline

or Amorphous structures exhibit

no long range periodic shapes
Xtal Systems not structures but potentials
FCC, BCC and HCP common Xtal Structures for
metals

Point, Direction and Planer IDing in Xtals

X-Ray Diffraction and Xtal Structure

Energy and Packing

Non dense, random packing

Energy
typical neighbor
bond length

typical neighbor
bond energy

r
Energy

Dense, ordered packing

typical neighbor
bond length

typical neighbor
bond energy

Dense, ordered packed structures tend to have

lower energies & thus are more stable.

CRYSTAL STRUCTURES
Crystal Structure

Means: PERIODIC ARRANGEMENT OF ATOMS/IONS

OVER LARGE ATOMIC DISTANCES
Leads to structure displaying
LONG-RANGE ORDER that is
Measurable and Quantifiable

All metals, many ceramics, and some

polymers exhibit this High Bond
Energy and a More Closely Packed
Structure

Materials Lacking Long range order

Amorphous Materials

These less densely

packed lower bond
energy structures
can be found in Metals
are observed in
Ceramic GLASS and
many plastics

Crystal Systems Some

Definitional information
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
7 crystal systems of varying
symmetry are known
These systems are built by
changing the lattice
parameters:
a, b, and c are the edge
lengths
, , and are interaxial
angles
Fig. 3.4, Callister 7e.

Crystal Systems
Crystal structures are divided
into groups according to unit
cell geometry (symmetry).

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

Have the simplest crystal structures.

We will examine three such structures (those of
engineering importance) called: FCC, BCC and
HCP with a nod to Simple Cubic

Crystal Structure of Metals of

engineering interest

Simple Cubic Structure (SC)

Rare due to low packing density (only Po Polonium -has this structure)

Close-packed directions are cube edges.

Coordination No. = 6
(# nearest neighbors)
for each atom as seen
(Courtesy P.M. Anderson)

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
Adapted from Fig. 3.23,
Callister 7e.

APF =

volume
atom
4
(0.5a) 3
1
3
a3

volume
unit cell

Here: a = Rat*2
Where Rat is the handbook
atomic radius

Body Centered Cubic Structure (BCC)

Atoms touch each other along cube diagonals within a
unit cell.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

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

Coordination # = 8
(Courtesy P.M. Anderson)

Adapted from Fig. 3.2,

Callister 7e.

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

Atomic Packing Factor: BCC

3a

a
2a

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

atoms
volume
4
( 3a/4) 3
2
unit cell
atom
3
APF =
volume
Adapted from
3
a
Fig. 3.2(a), Callister 7e.
unit cell
APF for a body-centered cubic structure = 0.68

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 7e.

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

(Courtesy P.M. Anderson)

Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74
The maximum achievable APF!
2a

a
Adapted from
Fig. 3.1(a),
Callister 7e.

Close-packed directions:
length = 4R = 2 a
(a = 22*R)

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
atoms
volume
4
( 2a/4) 3
4
unit cell
atom
3
APF =
volume
a3
unit cell

Hexagonal Close-Packed Structure (HCP)

ex: Cd, Mg, Ti, Zn
ABAB... Stacking Sequence
3D Projection

2D Projection
A sites

Top layer

B sites

Middle layer

A sites
a

Bottom layer

Adapted from Fig. 3.3(a),

Callister 7e.

Coordination # = 12

6 atoms/unit cell
APF = 0.74

c/a = 1.633 (ideal)

We find that both FCC & HCP are highest density packing
schemes (APF = .74) this illustration shows their
differences as the closest packed planes are built-up

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
= 6.023 x 1023 atoms/mol

Theoretical Density,

R
atoms
unit cell

=
volume
unit cell

Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
a = 4R/3 = 0.2887 nm

a
theoretical

2 52.00
a3 6.023 x 1023

g
mol actual
atoms
mol

= 7.18 g/cm3
= 7.19 g/cm3

Locations in Lattices: Point Coordinates

z

Point coordinates for unit cell

center are

111

a/2, b/2, c/2

000

a
x

Point coordinates for unit cell

(body diagonal) corner are 111

2c

b
b

Translation: integer multiple of

lattice constants identical
position in another unit cell

Crystallographic Directions
Algorithm

y
x

1. Vector is repositioned (if necessary) to

pass through the Unit Cell origin.
2. Read off line projections (to principal axes
of U.C.) in terms of unit cell dimensions a, b,
and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

[uvw]

ex: 1, 0, => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ]

where overbar represents a

negative index

families of directions <uvw>

What is this Direction ?????

Projections:
Projections in terms of a,b and c:
Reduction:
Enclosure [brackets]

x
a/2
1/2
1

y
b
1
2
[120]

z
0c
0
0

Linear Density considers equivalance and is

Number of atoms
important in Slip

Linear Density of Atoms LD =

[110]

Unit length of direction vector

ex: linear density of Al in [110]

direction
a = 0.405 nm

# atoms

LD
length

2
2a

3.5 nm 1

# atoms CENTERED on the direction of interest!

Length is of the direction of interest within the Unit Cell

Determining Angles Between Crystallographic

Direction:

u1u2 v1v2 w1w2

Cos
1

u v w u v w
2
1

2
1

2
1

2
2

2
2

2
2

Where uis , vis & wis are the Miller Indices of the directions in
question
also (for information) If a direction has the same Miller Indices as
a plane, it is NORMAL to that plane

HCP Crystallographic Directions

z

Algorithm
1. Vector repositioned (if necessary) to pass

a2

a3
a1

through origin.
2. Read off projections in terms of unit
cell dimensions a1, a2, a3, or c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
a2
[uvtw]

ex:

, , -1, 0

-a3

a2
2

Adapted from Fig. 3.8(a), Callister 7e.

=>

[ 1120 ]

a3

dashed red lines indicate

projections onto a1 and a2 axes

a1
2

a1

HCP Crystallographic Directions

Hexagonal Crystals
4

parameter Miller-Bravais lattice coordinates are

related to the direction indices (i.e., u'v'w') in the 3
space Bravais lattice as follows.
z

[ u 'v 'w ' ] [ uvtw ]

1
(2 u ' - v ')
3
1

v
(2 v ' - u ')
3
t - ( u +v )

u
a2

a3
a1
Fig. 3.8(a), Callister 7e.

w w'

Computing HCP Miller- Bravais Directional Indices

(an alternative way):
We confine ourselves to the bravais
parallelopiped in the hexagon: a1-a2Z and determine: (u,vw)

Here: [1 1 0] - so now apply the

models to create M-B Indices
a2

a3
a1

u 1

2u ' v '
3

2 1 1
3

v 1

2 v ' u '
3

2 1 1
3

t u v 1
w w' 0
M-B Indices: [11 20]

3
3

1
1

3 2 3 2

Defining 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 (in cubic lattices this is direct)

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) families {hkl}

Crystallographic Planes -- families

Crystallographic Planes
example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1
1/1
1
1

4.

Miller Indices

(110)

example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1/2
1/
2
2

4.

Miller Indices

(100)

b
1
1/1
1
1

1/
0
0

z
c

a
x

1/
0
0

1/
0
0

a
x

Crystallographic Planes
z
example
1. Intercepts
2. Reciprocals
3.

Reduction

4.

Miller Indices

a
1/2
1/
2
6

b
1
1/1
1
3

(634)

c
c
3/4
1/
4/3

4 a
x

Family of Planes {hkl}

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

Determine the Miller indices for the plane shown in the sketch

Intercepts
Intercept in terms of lattice parameters
Reciprocals
Reductions
Enclosure

-b
-1
-1

c/2
1/2
2

N/A

(012)

Crystallographic Planes (HCP)

In hexagonal unit cells the same idea is used

z

example
1. Intercepts
2. Reciprocals
3.

Reduction

a1
1
1
1
1

a2

1/
0
0

a3
-1
-1
-1
-1

c
1
1
1
1

a2

a3

4.

Miller-Bravais Indices

(1011)

a1
Adapted from Fig. 3.8(a), Callister 7e.

Crystallographic Planes

We want to examine the atomic packing of

crystallographic planes those with the
same packing are equivalent and part of
families
Iron foil can be used as a catalyst. The
atomic packing of the exposed planes is
important.
Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these
planes.
a)

Planar Density of (100) Iron

Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100)

4 3
R
3

Radius of iron R = 0.1241 nm

atoms
2D repeat unit

Planar Density =
area
2D repeat unit

1
a2

1
4 3
3

atoms
atoms
19
= 1.2 x 10
2 = 12.1
2
nm
m2

Atoms: wholly contained and centered in/on plane within U.C., area of plane in U.C.

Planar Density of (111) Iron

1/2 atom centered on plane/ unit cell

Solution (cont): (111) plane

2a

atoms in plane

nit

atoms above plane

r ep

ea

tu

atoms below plane

2D

3
a
2

Area 2D Unit: hb = *[(3/2)a][(2)a]=1/2(3)a2=8R2/(3)

atoms
2D repeat unit

Planar Density =
area
2D repeat unit

3*1/6

8R 2
3

= 7.0

atoms =
nm2

0.70 x 1019

atoms
m2

Adding Ionic Complexities

LOOKING AT THE CERAMIC

UNIT CELLS (CH 12)

Cesium chloride (CsCl) unit cell showing (a) ion positions and the two
ions per lattice point and (b) full-size ions. Note that the Cs +Cl pair
associated with a given lattice point is not a molecule because the ionic
bonding is nondirectional and because a given Cs+ is equally bonded to
eight adjacent Cl, and vice versa. [Part (b) courtesy of Accelrys, Inc.]

Sodium chloride (NaCl)

structure showing (a) ion
positions in a unit cell,
(b) full-size ions, and (c)
many adjacent unit cells.
[Parts (b) and (c)
courtesy of Accelrys,
Inc.]

Fluorite (CaF2) unit cell showing (a) ion positions and (b) full-size ions.
[Part (b) courtesy of Accelrys, Inc.]

SiO44

SiO44

Polymorphism: Also in Metals

Two or more distinct crystal structures for the

same material (allotropy/polymorphism)
iron system:
titanium
liquid
(HCP), (BCC)-Ti
1538C
-Fe
BCC
carbon:
1394C
diamond, graphite
-Fe
FCC
912C
BCC

-Fe

The corundum (Al2O3) unit cell is shown superimposed on the repeated

stacking of layers of close-packed O2 ions. The Al3+ ions fill two-thirds
of the small (octahedral) interstices between adjacent layers.

Exploded view of the kaolinite unit cell, 2(OH)4Al2Si2O5. (From F. H.

Norton, Elements of Ceramics, 2nd ed., Addison-Wesley Publishing
Co., Inc., Reading, MA, 1974.)

Transmission electron
micrograph of the structure
of clay platelets. This
microscopic-scale structure
is a manifestation of the
layered crystal structure
shown in the previous slide.
(Courtesy of I. A. Aksay.)

(a) An exploded view of the graphite (C) unit cell. (From F. H. Norton, Elements
of Ceramics, 2nd ed., Addison-Wesley Publishing Co., Inc., Reading, MA,
1974.) (b) A schematic of the nature of graphites layered structure. (From W.
D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction to Ceramics, 2nd
ed., John Wiley & Sons, Inc., NY, 1976.)

(a) C60 molecule, or

buckyball. (b) Cylindrical
array of hexagonal rings of
carbon atoms, or
buckytube. (Courtesy of
Accelrys, Inc.)

Arrangement of polymeric chains in the unit cell of polyethylene. The

dark spheres are carbon atoms, and the light spheres are hydrogen
atoms. The unit-cell dimensions are 0.255 nm 0.494 nm 0.741 nm.
(Courtesy of Accelrys, Inc.)

Weaving-like pattern of folded polymeric chains that occurs in thin

crystal platelets of polyethylene. (From D. J. Williams, Polymer Science
and Engineering, Prentice Hall, Inc., Englewood Cliffs, NJ, 1971.)

Diamond cubic unit cell showing (a) atom positions. There are two
atoms per lattice point (note the outlined example). Each atom is
tetrahedrally coordinated. (b) The actual packing of full-size atoms
associated with the unit cell. [Part (b) courtesy of Accelrys, Inc.]

Zinc blende (ZnS) unit cell

showing (a) ion positions. There
are two ions per lattice point (note
the outlined example). Compare
this structure with the diamond
cubic structure (Figure 3.20a). (b)
The actual packing of full-size
ions associated with the unit cell.
[Part (b) courtesy of Accelrys,
Inc.]

Densities
of
Material
Classes
In general

metals > ceramics > polymers

30
Why?
Metals have...

Ceramics have...
less dense packing
often lighter elements

Polymers have...

(g/cm3 )

close-packing
(metallic bonding)
often large atomic masses

low packing density

(often amorphous)
lighter elements (C,H,O)

Composites have...
intermediate values

Metals/
Alloys

20

Platinum
Gold, W
Tantalum

10

Silver, Mo
Cu,Ni
Steels
Tin, Zinc

5
4
3
2
1

0.5
0.4
0.3

Titanium
Aluminum
Magnesium

Graphite/
Ceramics/
Semicond

Polymers

Composites/
fibers

*GFRE, CFRE, & AFRE are Glass,

Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
60% volume fraction of aligned fibers
in an epoxy matrix).
Zirconia
Al oxide
Diamond
Si nitride
Glass -soda
Concrete
Silicon
Graphite

PTFE
Silicone
PVC
PET
PC
HDPE, PS
PP, LDPE

Glass fibers
GFRE*
Carbon fibers
CFRE*
Aramid fibers
AFRE*

Wood
Data from Table B1, Callister 7e.

Crystals as Building Blocks

Some engineering applications require single crystals:
--diamond single
crystals for abrasives
(Courtesy Martin Deakins,
GE Superabrasives,
Worthington, OH. Used with
permission.)

--turbine blades
Fig. 8.33(c), Callister 7e.
(Fig. 8.33(c) courtesy
of Pratt and Whitney).

Properties of crystalline materials

often related to crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than
others.

(Courtesy P.M. Anderson)

Polycrystals
Most engineering materials are polycrystals.

1 mm
Nb-Hf-W plate with an electron beam weld.
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).

Anisotropic

Adapted from Fig. K,

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

Isotropic

Single vs Polycrystals
E (diagonal) = 273 GPa
Single Crystals

-Properties vary with

direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:

Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)

-If grains are textured,

anisotropic.

Source of data is R.W.

Hertzberg, Deformation
and Fracture Mechanics
of Engineering
Materials, 3rd ed., John
Wiley and Sons, 1989.

E (edge) = 125 GPa

200 m
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].

Effects of Anisotropy:

X-Ray Diffraction

Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.
Cant resolve spacings
Spacing is the distance between parallel planes of
atoms.

Figure 3.32 Relationship of the Bragg angle () and the

experimentally measured diffraction angle (2).

X-ray
intensity
(from
detector)

d 2nsin
c

X-Rays to Determine Crystal Structure

Incoming X-rays diffract from crystal
d planes.

tg
u
o

ng
i
o

ys
a
-r

Measurement of
critical angle, c,
allows computation of
planar spacing, d.
For Cubic Crystals:

d hkl

or

1
g
in
m
co s
in ray
Xextra
distance
traveled
by wave 2

et
ec
t

Adapted from Fig. 3.19,

Callister 7e.

spacing
between
planes

X-ray
intensity
(from
detector)

h2 k 2 l 2

h, k, l are Miller Indices

reflections must
be in phase for
a detectable signal!

n
2 sin c

Figure 3.34 (a) An x-ray diffractometer. (Courtesy of

Scintag, Inc.) (b) A schematic of the experiment.

X-Ray Diffraction Pattern

z

Intensity (relative)

c
a
x

y (110)

a
x

c
b

a
x

(211)

(200)

Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.20, Callister 5e.

Diffraction in Cubic Crystals:

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).
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.

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.