Chapter 3

Crystal Structure
 Arrangement of Atoms
Arrangement of atoms determine
structure and properties of materials.
No order – atoms are random, e.g. gas.
Short-range order – atoms extend to
nearest neighbours, e.g. H2O, many
polymers.
Long-range order – regular, repetitive
arrangement of atoms that extend
throughout entire material, e.g. metals,
most ceramics and some polymers.
 No order Short range order

Short range order Long range order

Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers
crystalline SiO2
Adapted from Fig. 3.22(a),
Callister 7e.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
- many polymers

"Amorphous" = Noncrystalline noncrystalline SiO2

Adapted from Fig. 3.22(b),
Callister 7e.
 Crystal Structure
Crystal structure refers to the way in
which atoms, ions or molecules are
spatially arranged.
It is defined in terms of unit cell.
The crystal structure determines some
of the properties of crystalline solids.
 Unit Cell
A unit cell is the smallest structural unit or
building block that can describe the crystal
structure.
Repetition of the unit cell generates the entire
crystal.
The 3 dimensional framework is described by
a space lattice.
 Lattice parameters
The size and shape of the unit cell can be
described by lattice parameters or lattice
constants.
Axial lengths – a, b, c
Inter-axial angles – α, β, γ

Fig. 3.4, Callister 7e.

There are 4 types of unit cells:
(a) simple
(b) body centred
(c) face centred
(d) base centred

(a) (b) (c) (d)

 Metallic Crystal Structures
Metals are usually polycrystalline.
The atomic bonding in metals is non-
directional.
Dense atomic packing.
“Hard-sphere“ model where all atoms
are identical and thought of as being
solid spheres having well-defined
diameters with nearest neighbour atoms
touching each other.
 Simple Cubic Structure (SC)
Rare due to low packing density (only Po has this
structure).
Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbours)

1 atom/unit cell: 8 corners x 1/8

Atomic Packing Factor (APF) for
SC
Volume of atoms in unit cell
APF =
Volume of unit cell

4 / 3πr 3
APF = (1)
a a3
r 4 / 3π ( a / 2 ) 3
=
a3
close-packed directions = 0.52
a = 2r
 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 (α ), Tantalum, Molybdenum
• Coordination # = 8

Adapted from Fig. 3.2,

Callister 7e.

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

 APF for BCC
Volume of atoms in unit cell
APF =
Volume of unit cell

4 / 3πr 3
APF = (2)
a3
4 / 3π ( 3a / 4) 3
r = (2)
a a3
4r
= 0.68
a=
3
 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 1/2 + 8 corners x 1/8

 APF for FCC
Volume of atoms in unit cell
APF =
Volume of unit cell

4 / 3πr 3
APF = (4)
2a a3
4 / 3π ( 2a / 4) 3
= (4)
a a3
4r = 0.74
a=
2
 Hexagonal Close-Packed Structure
(HCP)

• Coordination # = 12 ex: Cd, Mg, Ti,

Zn
• c/a = 1.633
 APF for HCP

6( 4 / 3)πr 3
6 atoms/unit cell = 3 center + 2 APF =
3( 3 / 2) a 2 c
face x 1/2 + 12 corner x 1/6.
( 4 / 3)π ( a / 2) 3
= (2)
Vol. of atoms = (6) (4/3)πr3 ( 3 / 2) a 2 (1.6333 a )
Area of HCP base = (6)x(½ao2
= 0.74
sin 60o)
Vol. of HCP unit cell = 3 (ao2
sin60o)x c
 Close-packed Structures
Both FCC and HCP crystal structures
have highest atomic factors of 0.74.
Both FCC and HCP are generated by
stacking of close packed planes.
The difference between the two
structures is in the stacking sequence.
HCP: ABABABABAB…..
FCC: ABCABCABCABC……
 A sites

A c B sites
B
C
A sites
a
Volume, Linear & Planar
Density
Volumetric density = mass/unit cell
(ρV) Volume/unit cell

Linear density = No. of atomic dia. intersected by length of

line
(ρL) Length of the line contained in unit cell

Planar density = No. of atoms centred on plane of unit cell

(ρP) Area of plane contained in unit cell
 Theoretical Density, ρ
Mass of Atoms in Unit Cell
Density = ρ =
Total Volume of Unit Cell

nA
ρ =
VC NA

where n = number of atoms/unit

cell
A = atomic weight
VC = Volume of unit cell = a3 for
cubic
NA = Avogadro’s number
= 6.023 x 1023 atoms/mol
 Example: Volumetric density of Cr
(BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2

R a = 4R/ 3 = 0.2887 nm
a

atoms
g
unit cell 2 52.00
mol ρ theoretical = 7.18 g/cm3

ρ = ρ = 7.19 g/cm3
a 3 6.023 x 1023
actual

volume atoms

unit cell mol

 Example: Linear density for FCC
Linear density = No. of atomic dia. intersected by length
of line
(ρL) Length of the line contained in unit
cell

2 1
LD110 = =
4R 2R
Example: Planar density for FCC
Planar density = No. of atoms centred on
plane of unit cell
(ρP) Area of plane contained in
unit cell

(1 / 4)(4) + (1 / 2)(2) 2
PD110 = =
4 R(2 2 R) 4 2R 2
 Densities of Material Classes
In general Metals/
Graphite/
Composites/
ρ ρ ρ Ceramics/ Polymers
metals > ceramics > polymers Alloys
Semicond
fibers
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
(metallic bonding) Cu,Ni
in an epoxy matrix).
Steels
• often large atomic masses Tin, Zinc
Zirconia

(g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
Diamond
• less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2
Polymers have... Magnesium Carbon fibers
ρ

Graphite CFRE*
Silicone Aramid fibers
PVC
• low packing density PET AFRE*
1 PC
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• intermediate values 0.3

Data from Table B1, Callister 7e.
 Allotropy & Polymorphism
Some materials may exist in different
crystal structure under different
conditions of temperature/pressure; this is
called polymorphism.

If the material is an elemental solid, it is

called allotropy.
 Examples
Allotropic crystalline forms
of iron o
Titanium C
α , β -Ti Liquid iron
1539
δ (delta) iron (BCC)
1394
Carbon γ (gamma) iron (FCC)
diamond, graphite
912

α (alpha) iron (BCC)

-273
 Single Crystal &
Polycrystalline Materials
Single crystals – atoms are in a repeating or periodic
array over the entire extent of the material.
Polycrystalline material – comprised of many small
crystals or grains. The grains have different
crystallographic orientation. The regions where grains
meet are called grain boundaries.
Single crystal 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.
(Epolyiron = 210 GPa)
-If grains are textured,
anisotropic.
E (diagonal) = 273 GPa
Data from Table 3.3,
Callister 7e.
(Source of data is R.W.
Hertzberg, Deformation
and Fracture Mechanics
of Engineering
Materials, 3rd ed., John
Wiley and Sons, 1989.)
200 µ m Adapted from Fig.
4.14(b), Callister 7e.
(Fig. 4.14(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].)
 Anisotropy
Anisotropic behaviour – properties of
materials depend on directionality.
E.g. Graphite
Above 3000oC, coefficient of thermal
expansion along c axis is > 25 times
greater than direction parallel to basal
planes.
Other examples: wood, steel-reinforced
concrete, carbon fibre-reinforced epoxy.
 Points in Unit Cell
z

0, 0, 1

 Right handed coordinate

system.
x – coming out of paper. 1, 1, 1
y – right of paper.
z – to the top.
 Negative directions in ½, ½, ½
opposite manner.
 Notation used – distances
0, 0, 0
y
separated by comma.
½, 1, 0
1, 0, 0
1, 1, 0
x
 Crystallographic Directions
Miller indices for directions:
a)Determine coordinates of two points in
direction of interest.
b)Subtract coordinates of 1st point from 2nd .
c)Clear fractions and reduce to lowest
integer.
d)Enclose in square brackets [uvw].
Negative direction index – bar over
number,
e.g. [0 1 0].
 Example z Direction Indices

OA [100]
F
OB [110]
C
OC [111]

D OD [201]
E y
OE [010]
O
OF [112]
A
B
x CB [001]
Directions are crystallographically equivalent
if the atom spacing along each direction is the
same.
E.g. [100], [010], [001], [010], [001], [100]
Equivalent directions are called indices of a
z
family or form.
Notation used: <100>

y
O

x
 Example for HCP
Miller-Bravais indices is used to describe directions and
planes for hexagonal unit cell.
3 index notation a1, a2 and z (a3 axis is redundant) is used
for direction, with the same procedure as cubic system.

Algorithm

1. Point 2: 1,1,0 and Point 1:

a2 0, 0, 0
2. Subtracting results in 1, 1,
- 0.
a3 [110]
3. No fractions to clear.
a1
4. Enclose in square brackets,
Adapted from Fig. 3.8(a), Callister 7e.
no
The 3 axis can be converted to 4 axis
notation.
In the 4-axis notation [uvtw], the first three
relate to a1, a2 and a3 axes, while w relates to
c axis.
z [ u ' v ' w ' ] → [ uvtw ]

1
u = ( 2 u ' - v ')
3
1
a2 v = ( 2 v ' - u ')
3
- t = -(u +v )
a3
w = w '
a1
Adapted from Fig. 3.8(a), Callister 7e.
 Crystallographic Planes
Miller indices for planes:
a)Identify coordinate intercepts of the plane.
If plane is parallel to one of the axes –
consider as infinity. If plane passes through
origin, origin must be moved.
b)Form reciprocals of intercepts.
c)Clear fractions but do not reduce to lowest
integer.
d)Enclose numbers in parentheses (hkl).
 z

exampl a b c c
1.
e 1 1 ∞
Intercepts
2. 1/1 1/1 1/∞
Reciprocals 1 1 0 y
3. Clear 1 1 0 a b
fraction
4. Miller Indices x
(110) z
example a b c
1. 1/2 ∞ ∞ c
2.
Intercepts 1/½ 1/∞ 1/∞
Reciprocals 2 0 0
3. Clear 2 0 0 y
fraction
4. Miller Indices
a b

(100) x
 z

example a b c c
1. Intercepts 1/2 1 3/4 •
2. 1/½ 1/1 1/¾
Reciprocals 2 1 4/3 • y
• b
3. Clear 6 3 4 a
fraction x
4. Miller Indices
(634)

Family of Planes
{hkl}
Ex: {100} = (010),(001),(100),(010),(001)
(100),
If sets of equivalent lattice planes are
related by symmetry of the crystal system,
they are called planes of a family or form.
Notation used: {hkl}
E.g. (100), (010), (001), (010), (001), (100)
In cubic crystals, a plane and a direction
with same indices are orthogonal.
 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. Clear fraction 1 0 -1 1
a3

4. Miller-Bravais Indices (1011) a1

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

Sometimes HCP planes are identified by (hkl) only

because h + k = -i.
Close-packed Planes &
Directions

Structure Directions Planes

SC <100> None
BCC <111> None
FCC <110> {111}
HCP <100>, (0001), (0002)
<110>
 Interstices

Interstices describe spaces or holes between

atoms in which smaller atoms could fit.
Filled by impurities or small alloying atoms.
Cubic interstitial site has CN = 8.
Octahedral site has CN = 6.
Tetrahedral site has CN = 4.
Determination of size of interstitial sites in
terms of size of atoms at regular lattice
points.
E.g. Find the radius of atom that will fit into
octahedral site in FCC structure:
2 R +2r = 4 R / 2
r
= 0.414
R
 X-ray Diffraction
Crystal structures are determined by x-ray
diffraction (XRD).

When incident beam of monochromatic x-

rays of wavelength λ strikes crystal planes
at an angle θ such that wave patterns
leaving the crystal are in phase, diffraction
occurs.
Condition for diffractionnλ
: = SQ + QT

nλ = d hkl sin θ + d hkl sin θ

= 2d hkl sin θ
This is known as Bragg’s law :
2d sinθ = nλ
where d = interplanar spacing,
n = order of diffraction, 1, 2, 3,...

To calculate lattice parameter for cubic

crystal,
a = d hkl h + k + l
2 2 2
Rules for determining diffracting {hkl}
planes in cubic crystals.

SC – all (hkl) planes are possible.

BCC – (h+k+l) total to even number.
FCC – (h,k,l) all odd or all even.
Diffraction Techniques
- Uses a diffractometer.
- X-rays are generated at T.
- Diffracted beams are detected at
C.
- Rotation of specimen through
angle θ is accompanied by a 2θ
rotation of the counter.
Example:
For BCC iron, compute (a) the interplanar
spacing and (b) the diffraction angle for the
(220) set of planes. The lattice parameter
for Fe is 0.2866nm. Also, assume that
monochromatic radiation having a
wavelength ofa0.1790nm is used,
0.2866 nm and the
of =reflection
orderd hkl h +k +l
2 2 is
2
=1.
2 +2 +0
2 2 2
= 0.1013 nm

(a)
nλ (1)(0.1790 nm)
sin θ = = = 0.884
2d hkl (2)(0.1013 nm)
(b) θ = sin −1 (0.884) = 62.13o
∴ 2θ = 124.26 o
 Summary
• Atoms may assemble into crystalline or
amorphous
• structures.
Common metallic crystal structures are FCC,
BCC, and
HCP. Coordination number and atomic
packing
• We can factor
predict the density of a material,
are thewe
provided same for both FCC and HCP crystal
structures.
know the atomic weight, atomic radius, and
crystal
• Crystallographic points, directions and
geometry
planes are (e.g., FCC, BCC, HCP).
specified in terms of indexing schemes.
Crystallographic directions and planes are
related
to atomic linear densities and planar
 Summary
• Materials can be single crystals or
polycrystalline.
Material properties generally vary with single
crystal
orientation (i.e., they are anisotropic), but are
generally
• Some materials can have more than one
non-directional (i.e., they are isotropic) in
crystal
polycrystals
structure. This is referred to as
with randomly
polymorphism (ororiented grains.
• X-ray diffraction is used for crystal structure
andallotropy).
interplanar spacing determinations.
 Study Checklist
After this chapter, you should be able
to:
Explain the difference between crystalline and non-crystalline structures.
Draw unit cells for BCC, FCC and HCP structures; identify or draw directions and
planes.
Determine density or lattice parameters from given data.
To define isotropy and anisotropy in terms of material properties.
To define polymorphism or allotropy, with example.
To calculate interplanar spacing for crystallographic planes responsible for the
diffraction peak.