TOPIC 3

Crystal Structures
&
Properties

1
 Topic Contents
Introduction
Arrangement of atom in metallic crystal structures.
Crystallographic point, plane and direction.
Linear & Planar density.
Single crystal, polycrystalline materials
X-ray diffraction: determination of crystal structure.

2
 TOPIC OUTCOMES
At the end of the lecture, students will be able:
1. To describe the difference in atomic/molecular structure
between crystalline and noncrystalline materials.
2. To draw unit cells for face-centered cubic (FCC), body-
centered cubic (BCC) structures.
3. To derive the relationships between unit cell edge length
and atomic radius for FCC and BCC crystal structures.
4. To compute the densities for metals having FCC and BCC
crystal structures given their unit cell dimensions.
5. To give 3 direction index integers, sketch the direction
corresponding to these indices within a unit cell.

3
 TOPIC OUTCOMES
6. To specify the Miller indices for a plane that has been
drawn within a unit cell.
7. To describe how FCC crystal structures may be generated
by the stacking of close-packed planes of atoms.
8. To distinguish between single crystals and polycrystalline
materials.
9. To describe briefly the phenomenon of diffraction.
10. To compute interplanar spacing for the crystallographic
planes that are responsible for the diffraction peak.
11. To define isotropy and anisotropy with respect to material
properties.

4
 (1) INTRODUCTION
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?

5
 (1) INTRODUCTION
ENERGY AND PACKING
• Non dense, random packing

• Dense, regular packing

Dense, regular-packed structures tend to have lower energy.

6
Solid materials:
Classified according to the regularity with which
atoms or ions are arranged with respect to one
another.
2 types:
Crystalline materials
Noncrystalline (or amorphous) materials

7
(2) ARRANGEMENT OF ATOMS
In Crystal Structure

Crystal structure:
Atoms, ions, or molecules are spatially arranged

Noncrystalline materials...
• atoms have no periodic or repeating packing.
• crystal has no long range order.
• occurs for:
-complex structures
-rapid cooling
"Amorphous" = Noncrystalline
noncrystalline SiO2

8
Crystalline materials...
• atoms pack in periodic (or repeating), 3D
arrays, over large atomic distances (long
range order)
• typical of: -metals
-many ceramics
-some polymers

crystalline SiO2

There is an extremely large number of different crystal

structures all having long range atomic order, depending
how you ARRANGE and PACK it.

9
TEM micrograph showing a lattice image of zinc-blende crystal structure of GaAs
(A. Trampert and O. Brandt)

10
TEM micrograph showing a crystalline grain of Si that is embedded in a matrix of
amorphous Si
(J. Lutzen et al – J. Vac. Sci. Technol. 16, 2802 (1998))

11
 How to describe a crystal structure ?
Basic structural unit of s
A periodic crystal structure.
array of Entities of atoms, An arrangement of atoms,
Atoms located within a
points ions or molecules ions or molecules around
the lattice site. parallelepiped (or prisms)
volume
Lattice Basis Crystal structure
Unit Cell
b0
+ =
a0 Building block of
crystal structure

+ =

Crystal structure may be broken down into a lattice and a basis.

Lattice points (space lattice) correspond to the vertices of dashed lines.
Both crystal structures exhibit same lattice structure but differ in the
details of their basis unit.
a0 and b0 = lattice constants
12 in
2 dimensions & 3-dimensions. two different directions
How many types of crystal structures are available?

How many types of unit cell?

Depends on types of lattices.

There is an unlimited number of possible lattices because there is no

natural restriction on the lengths of lattice translation vectors or on
the angle  between them.

3 primary directional length + 3 angles between the 3 directions ➔

type of unit cell
Three-dimensional Lattice Types:
14 Bravais lattices a3
14 types of unit cells
14 types of Crystal Structures
a2 

 a1
13
Assumptions used to describe crystal
structure:

When describing crystalline structures,

atoms (or ions) are thought of as being
solid spheres having well defines
diameters.
This is termed the atomic hard sphere
model in which spheres representing
nearest-neighbour atoms touch one
another.
14
Three-dimensional
Lattice Types:

15
 The 14 lattice types in 3-D
Number of Restriction on conventional cell
Crystal system
lattices axes and angles

a1  a2  a3
Triclinic 1

a1  a2  a3
Monoclinic 2
 =  = 90o  
a1  a2  a3
Orthorhombic 4
 =  =  = 90o
a1 = a2  a3
Tetragonal 2
 =  =  = 90o
a1 = a2 = a3
Cubic 3
 =  =  = 90o
a1 = a2 = a3
Trigonal 1
 =  =  < 120o,  90o
a1 = a2  a3
Hexagonal 1 =  = 90o
16
 = 120o
 Metallic Crystal Structure

• tend to be densely packed.

• have several 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.
• have the simplest crystal structures.
We will look at three (3) such structures...

simple cubic (SC) body-centered cubic face-centered cubic

17
(BCC) (FCC)
 SIMPLE CUBIC STRUCTURE (SC)

• Rare due to poor packing (only Po has this structure)

• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson) 18

 8 Unit Cells 1 Unit Cell

No. of Atom in UNIT CELL = 1 atom

19
ATOMIC PACKING FACTOR

• APF for a simple cubic structure = 0.52

20
 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.

21
 • Coordination # = 8

(Courtesy P.M. Anderson) 22

 ATOMIC PACKING FACTOR: BCC
• APF for a body-centered cubic structure = 0.68

Unit cell contains:

1 + 8 x 1/8
= 2 atoms/unit cell
R
Adapted from a
Fig. 3.2,
Callister 6e.

23
Example 1:
Calculate the volume of a BCC cell with atomic radius of R.

a2 + (a√2)2 = (4R)2
a a = 4R/√3
4R
Isipadu = a3
= (4R/√3 )3
a√2
24
Example 2:

Prove the APF of BCC = 0.68

APF = V atom/ V unit cell

V atom = (2)(4/3πR3) = 8.373R3
V unit cell = a3
= (4R/√3 )3
= 12.32 R 3

APF = 8.373R3 / 12.32 R 3

= 0.68

25
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.

26
(Courtesy P.M. Anderson)

27
Coordination number of
FCC

Coordination number = 12
28
 Length of closed pack
direction = 4R = √2a

Equivalent number of atom = 6 x

1/2 + 1/8 x 8 = 4 atom/unit
29
 ATOMIC PACKING FACTOR: FCC
• APF for a body-centered cubic structure = 0.74

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a

30
Example 3:
Calculate the volume of a FCC cell with atomic radius of R.

a2 + a2 = (4R)2
a = 4R/√2
a 4R volume = a3
= (4R/√2)3

31
 FCC STACKING SEQUENCE
• ABCABC... Stacking Sequence
• 2D Projection
A
B B
C
A
A sites B B B
C C
B sites B B
C sites

• FCC Unit Cell

32
11
STRUCTURE OF COMPOUNDS: NaCl
• Compounds: Often have similar close-packed structures.
• Structure of NaCl • Close-packed directions
--along cube edges.

33
THEORETICAL DENSITY, r

34
Example 5: 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 = 10-7 cm)

Result: theoretical rCu = 8.89 g/cm3

Compare to actual: rCu = 8.94 g/cm3
35
Characteristics of Selected Elements at 20oC
At. Weight Density Atomic radius
Element Symbol (amu) (g/cm3) (nm)
Aluminum Al 26.98 2.71 0.143
Argon Ar 39.95 ------ ------
Barium Ba 137.33 3.5 0.217
Beryllium Be 9.012 1.85 0.114
Boron B 10.81 2.34 ------
Bromine Br 79.90 ------ ------
Cadmium Cd 112.41 8.65 0.149
Calcium Ca 40.08 1.55 0.197
Carbon C 12.011 2.25 0.071
Cesium Cs 132.91 1.87 0.265
Chlorine Cl 35.45 ------ ------
Chromium Cr 52.00 7.19 0.125
Cobalt Co 58.93 8.9 0.125
Copper Cu 63.55 8.94 0.128
Flourine F 19.00 ------ ------
Gallium Ga 69.72 5.90 0.122
Germanium Ge 72.59 5.32 0.122
Gold Au 196.97 19.32 0.144
Helium He 4.003 ------ ------
Hydrogen H 1.008 ------ ------ 36
 DENSITIES OF MATERIAL CLASSES
Why?
Metals have...
• close-packing
(metallic bonding)
• large atomic mass
Ceramics have...
• less dense packing
(covalent bonding)
• often lighter elements
Polymers have...
• poor packing
(often amorphous)
• lighter elements (C,H,O)
Composites have...
Data from Table B1, Callister 6e.
• intermediate values 37
 HEATING AND
COOLING OF AN IRON WIRE
• Demonstrates "polymorphism"
allotropy
The same atoms can
have more than one
crystal structure.
38
 Topic Contents

Introduction
Arrangement of atom in metallic crystal structures.
Crystallographic point, plane and direction.
Linear & Planar density.
Single crystal, polycrystalline materials
X-ray diffraction: determination of crystal structure.

39
 Crystal System
Crystallographic Points
Crystalline materials
Point Coordinates, xyz

Crystalline materials
Point Coordinates, xyz

40
EXAMPLE 6

41
EXAMPLE 7

42
Crystallographic Directions
Crystallographic Directions
Defined as a line between two points, or
Defined as a vector
[uvw] – square bracket
All parallel direction vectors have the same direction
indices.

43
Directions are said to be crystallographically equivalent if the
atom spacing along each direction is the same.

Equivalent directions are called indices of a family.

[100], [010], [001], [010], [001], [100]  <100> (cubic system).

This is, in general, not true for other crystal system. For
example, for crystals of tetragonal symmetry, [100] and [010]
directions are equivalent, whereas [100] and [001] are not.

Hexagonal crystals:

Four-axis or Miller-Bravais coordinate system.

44
EXAMPLE 8

45
EXAMPLE 9

46
Crystallographic Planes
Specified by three Miller indices as (hkl) or (hkil)

47
Procedures to determine a crystallographic plane:
(1) If the plane passes through the selected origin, either
another parallel plane must be constructed within the unit cell
by an appropriate translation, or a new origin must be
established at the corner of another unit cell.
(2) At this point the crystallographic plane either intersects or
parallels each of the three axes; the length of the planar
intercept for each axis is determined in terms of the lattice
parameters a, b, and c.
(3) The reciprocals of these numbers are taken. A plane that
parallels an axis may be considered to have an infinite
intercept, and, therefore a zero index.
(4) If necessary, these 3 numbers are changed to the set of
smallest integers by multiplication or division by a common
factor.
(5) Finally, the integer indices, not separated by commas, are
enclosed within parentheses, thus: (hkl). 48
 EXAMPLE 11
Draw the crystallographic planes of (101) and (221) for a simple
cubic cell.

(101)
1. Determine the origin
Z 2. Reciprocals :
1/1, 1/0, 1/1 = 1, ∞, 1

The plane is intercepted at

axes of X and Z = 1; and
parallel to Y-axis.

origin Y

X 49
 (221)

1. Determine the origin

Z 2. Reciprocals :
1/2, 1/2, 1/1 = 1/2, 1/2, 1

The plane is intercepted at axes

of X = ½, Y = ½, and Z = 1

origin Y

X 50
 Question
Determine the crystallographic plane labeled as A
in the following figure.

Plane
A
Y

X 51
 Answer
1. Determine the origin

2. The plane is intercepted at axes

of X = 1, Y = 1, and Z = 
Z
3. Reciprocals :
1, 1, 0

4. (110)
Plane
A
Y

52
X
 Topic Contents

Introduction
Arrangement of atom in metallic crystal structures.
Crystallographic point, plane and direction.
Linear & Planar density.
Single crystal, polycrystalline materials
X-ray diffraction: determination of crystal structure.

53
Linear Density
Linear density (LD) = the number of atoms per unit length whose
centers lie on the direction vector for a specific crystallographic
direction

# atoms centered on direction vector

LD =
Length of direction vector

54
Example:

LD110 = 2 atom/4R
= 1/2R
55
 Planar Density (PD)
number of atoms centered on a planar
PD (nm-2) =
Area of a planar

PD110 = 2 atoms/(8R22) = 1/(4R22)

LD and PD are important ➔ slip process

56
 Topic Contents

Introduction
Arrangement of atom in metallic crystal structures.
Crystallographic point, plane and direction.
Linear & Planar density.
Single crystal and polycrystalline materials
X-ray diffraction: determination of crystal structure.

57
 CRYSTALS AS BUILDING BLOCKS
Single crystal ➔ Periodic and repeated arrangement of atoms is perfect
or extends throughout the entirety of specimen without interruption.

• Some engineering applications require single crystals:

--diamond single
--turbine blades
crystals for abrasives

• Crystal properties reveal features

of atomic structure.
--Ex: Certain crystal planes in quartz
fracture more easily than others. 58
semiconductor 59
 POLYCRYSTALS
• Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 6e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
1 mm

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

• Each "grain" is a single crystal.
• If crystals are randomly oriented,
overall component properties are not directional.
• Crystal sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers). 60
61
Stages of solidification of polycrystalline material
b) Growth of the crystallites; the
a) Small crystallite nuclei obstruction of some grains that are
adjacent to one another have formed

Unit cell

d) The grain structure as it would

c) Upon completion of
appear under the microscope
solidification, grains having
(dark lines are the grain 62
irregular shapes have formed
boundary)
 SINGLE vs POLYCRYSTALS
• 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.
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 mm 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].)
63
64
 Topic Contents

Introduction
Arrangement of atom in metallic crystal structures.
Crystallographic point, plane and direction.
Linear & Planar density.
Single crystal, polycrystalline materials
X-ray diffraction: determination of crystal
structure.

65
 X-ray Diffraction (XRD):
• Understand atomic and molecular arrangements in
solids.
• Crystal structures & type of materials.
• New materials development.

Issues to be addressed:
• How does X-ray diffract? (X-ray diffraction
phenomenon.)
• How to use X-ray?
• How to computer atomic interplanar distances?
• How to determine crystal structures via X-ray
diffraction technique? 66
 Diffraction Phenomenon
How diffraction occurs?
• When a wave encounters a series of regularly spaced
obstacles.
• Is a consequence of specific phase relationships
established between two or more waves that have
been scattered by the obstacles.

The obstacles:
• Capable of scattering the wave.
• Having spacings that are comparable in magnitude to
the wavelength ().
67
Phase relationship between scattered waves
• 3 situations:
• Constructive interference (in-phase)
• Destructive interference (out of phase)
• Partial constructive interference.

68
Constructive Interference

69
Destructive Interference

70
 X-Ray Diffraction
What is X-ray?
• A form of electromagnetic radiation
• Having high energy
• Having short wavelength () – in the order of atomic
spacings for solids.

71
• Incoming X-rays diffract from crystal planes.

• Parallel
• Monochromatic
• Coherent (in-phase)

= interplanar
hkl spacing

72
Miller indices: h,k,l
• Measurement of:
Critical angles, qc, for X-rays provide atomic spacing, d.

73
 Bragg’s Law

q q
C E

D
n = C D + D E
n = d hkl sin q + d hkl sin q = 2d hkl sin q
74
Bragg’s Law
Relationship among x-ray wavelength, interatomic
spacing, and angle of diffraction for constructive
interference.

If Bragg’s Law is not satisfied:

• Nonconstructive interference
• Very low intensity diffracted beam

75
Crystal structures of cubic symmetry

Lattice
a parameter

d hkl =
h +k +l
2 2 2

Interplanar
distance with
respect to
Miller indices,
h, k, l

76
Reflection Rules of XRD for the Common Metal Structures

Crystal Diffraction DOES NOT Diffraction

Structure Occur When: Occurs When:

h + k + l = even
BCC h + k + l = odd number
number
h, k, l unmixed
h, k, l mixed (both even
FCC (are all even or all
and odd numbers)
odd numbers)
(h = 2k) = 3n, I odd (n is
HCP All other cases
an integer)

77
Miller Indices of the Diffracting Planes for BCC and FCC Lattices

78
 Miller Indices of the Diffracting Planes for BCC and FCC Lattices

Cubic planes Cubic diffraction

planes {hkl}
{hkl} h2+k2+l2 (h2+k2+l2) FCC BCC
{100} 12+02+02 1 … …
{110} 12+12+02 2 … 110
{111} 12+12+12 3 111 …
{200} 22+02+02 4 200 200
{210} 22+12+02 5 … …
{211} 22+12+12 6 211
… …. 7 … …
{220} 22+22+02 8 220 220
{221} 22+22+12 9 … …
{310} 32+12+02 10 … 310
Interpreting experimental XRD data for
metals with Cubic Crystal
BCC: The first two sets of diffracting planes are {110} and
{200} planes
Sin2 θA = 12 + 12 + 02 = 0.5
Sin2 θB 22 + 02 + 02

FCC: The first two sets of diffracting planes are

{111} and {200} planes

Sin2 θA = 12 + 12 + 12 = 0.75
Sin2 θB 22 + 02 + 02
80
 Diffraction Techniques
• Powder diffraction method.
• Samples in powder or polycrystalline form.
• Having random oriented particles.
• Proper oriented particles ➔ crystallographic plane ➔
diffraction peak

81
82
83
84
EXAMPLE 13:
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 0.2866 nm. Also assume that
monochromatic radiation having a wavelength of 0.1790 nm
is used, and the order of reflection is 1.

(a)
a
d hkl =
h +k +l
2 2 2

0.2866
d hkl = = 0.1013 nm
2 +2 +0
2 2 2
85
 n
(b)
(1)(0.1790)
sin q = = = 0.884
2d hkl (2)(0.1013)
q = sin (0.884) = 62.13
−1 0

Diffraction angle = 2q = (2)(62.13o) = 124.26o

86
EXAMPLE 14:

• An x-ray diffractometer recorder chart for an

element which has either the BCC or the FCC
crystal structure shows diffraction peaks at the
following 2θ angles: 40, 58, 73.86.8, 100.4 and
114.7. The wavelength of the incoming x-ray
used was 0.154 nm.
a) Determine the cubic structure of the element
b) Determine the lattice constant of the element
c) Identify the element

87
(a)
2q (o) q (o) sin q sin2 q
40 20 0.3420 0.1170
58 29 0.4848 0.2350
73 36.5 0.5948 0.3538
86.8 43.4 0.6871 0.4721
100.4 50.2 0.7683 0.5903
114.7 57.35 0.8420 0.7090

sin2 q 0.1170 = 0.498 ≈ 0.5 (➔ BCC)

=
sin q 0.2350
2

If the ratio is 0.75 ➔ FCC

88
b)
sin2 θ = λ2 (h2 + k2 + l2)
4a2
a= 0.318 nm

c) Tungsten (a= 0.318 nm and BCC)

End of Topic 89