ENGG 103

Materials in Design

Structure of Crystalline Solids

Callister Chapter 3

15 March 2016
 The Structure of Crystalline Solids

ISSUES TO ADDRESS...

What is the difference in atomic arrangement

between crystalline and non-crystalline solids?

What features of a material’s atomic

structure determine its density?

Under what circumstances does a material

property vary with the measurement direction?

2
 Energy and Packing
Non dense, random packing Energy
typical neighbour
bond length

typical neighbour r
bond energy

Energy

Dense, ordered packing typical neighbor

bond length

typical neighbour r
bond energy

Dense, ordered packed structures tend to have

lower energies 3
 Materials and Packing
Crystalline materials
Atoms pack in periodic, 3D arrays

Typical of -metals
-many ceramics
crystalline SiO2
-some polymers

Si Oxygen
Non-crystalline materials
Atoms have no periodic packing
-complex structures
Typical of -rapid cooling

"Amorphous" = Noncrystalline noncrystalline SiO2

4
 Metallic Crystal Structures
How can we stack metal atoms to minimize empty space?
2-dimensions

vs.

Now stack these 2-D layers to make 3-D structures

5
 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.

6
 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)

7
 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
4
a unit cell 1 π (0.5a) 3
3
R = 0.5a APF =
a3 volume
close-packed directions unit cell
contains 8 x 1/8 = 1 atom/unit cell

8
 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
2 atoms/unit cell: 1 center + 8 corners x 1/8
9
VMSE Screenshot – BCC Unit Cell

10
 Atomic Packing Factor: BCC
APF for a body-centered cubic structure = 0.68

3a

2a

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

atoms volume
4
unit cell 2 π ( 3a/4 ) 3
3 atom
APF =
3 volume
a
unit cell 11
 Face Centered Cubic Structure (FCC)
Atoms touch each other along face diagonals.
All atoms are identical; the face-centered atoms are shaded differently only for
ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

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

Coordination # = 12
12
 Atomic Packing Factor: FCC
APF for a face-centered cubic structure = 0.74
Maximum achievable APF

Close-packed directions:
length = 4R = 2 a

2 Unit cell contains:

a 6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
atoms volume
4
unit cell 4 π ( 2a/4 ) 3
3 atom
APF =
3 volume
a
unit cell
13
 FCC Stacking Sequence
ABCABC... Stacking Sequence
2D Projection

B B
C
A
A sites B B B
C C
B sites B B
C sites

A
FCC Unit Cell B
C

14
VMSE Screenshot – Stacking Sequence and Unit
Cell for HCP

15
 Shared Atoms in a Unit Cell
Face centred cubic (fcc)
Important

Iron/Steel
(γ austenite [910 -1395C])

Al, Cu, Au, Pb, Ni, Pt, Ag

Body centred cubic (bcc)

Iron/Steel
α ferrite (below
[910C]

δ ferrite [1395 –
1538C]

Cr, Mo, W, V, Nb 16
 Structure of crystalline ceramics
In crystalline ceramics atoms are
arranged in regular patterns described Salt (NaCl) cubic structure
by the unit cell.

Molten rock
 Ceramics are (nearly always) compounds:
made up of two or more atom types
 Crystal structures are more complicated than
for metals.
 One exception is diamond, which is a
ceramic made from just carbon.
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 Directions in Unit Cells
Cartesian Co-ordinates
A (2D) Cartesian coordinate system is a coordinate system that
specifies each point uniquely in a plane by a pair of numerical
coordinates, which are the signed distances to the point from two fixed
perpendicular directed lines, measured in the same unit of length.

Three Dimensions
Two Dimensions
 Z Directions in a unit cell

X=1
Y=1
Z=1

Direction is
[111]

X
Important
19
 Z
X = 1/2
Y = 1/2
Z=1

Covert to whole numbers

X=½x2=1
Y=½x2=1
Z=1x2= 2

Direction is
[112]
X

20
 Planes in Unit Cells
Miller indices

Miller indices are used to describe a plane or set of

planes within a unit cell

The Miller indices for a plane are

 The reciprocals of the intercepts the plane makes with the
three axes
 Reduced to the smallest integers

The only planes that we shall be dealing with are the

planes with Miller indices (111) and (110)
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 Z
Important

X=1
Y=1
Z=1

1/X = 1
1/Y = 1
1/Z = 1

Y
Miller indices of
this blue plane is
(111)
X This is the most-densely packed plane in the
FCC-structure 22
 Z
Important

X=1
Y=1
Z=∞

1/X = 1
1/Y = 1
1/Z = 0

Y
Miller indices of
this blue plane is
(110)
X This is the most-densely packed plane in the
BCC-structure 23
Crystallographic Planes

24
 The (111) Plane in the FCC Unit Cell

Note
The (111) plane is the most densely packed plane in the FCC unit cell
The (110) Plane in the FCC Unit Cell
The [110] Direction in the FCC Unit Cell

Note
The [110] direction (XYZ) is the most densely packed
direction in the FCC unit cell

This direction lies in the (111) plane (AXZ) with B as origin

 The (110) Plane in the BCC Unit Cell

Note
The (110) plane (A”D”E”B”) is the most densely packed plane
in the BCC unit cell

The [111] direction (D’B’) is the most densely packed

direction in the BCC unit cell
Formation of Crystals during Solidification

Growth of
Formation of Nuclei
nuclei

Final crystal
Nuclei structure as
impinge upon observed
each other under a
microscope

Upon solidification, solid crystals nucleate in the liquid and

grow until they impinge upon each other
 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
= 6.022 x 1023 atoms/mol

30
 2R Theoretical Density, ρ

Example: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell

R a = 4R/ 3 = 0.2887 nm
a

atoms
g
unit cell 2 52.00 ρtheoretical = 7.18 g/cm3
mol
ρ= ρactual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol 31
 Densities of Material Classes
In general
Graphite/
ρmetals > ρceramics > ρpolymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
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Why? B ased on data in Table B1, Callister
20 Platinum *GFRE, CFRE, & AFRE are Glass,
Metals have... Gold, W
Tantalum Carbon, & Aramid Fiber-Reinforced
• close-packing Epoxy composites (values based on
60% volume fraction of aligned fibers
(metallic bonding) 10 Silver, Mo in an epoxy matrix).
Cu,Ni
• often large atomic masses Steels
Tin, Zinc
Zirconia

ρ (g/cm3 )
Ceramics have... 5
Titanium
4 Al oxide
Diamond
• less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2 Carbon fibers
Magnesium G raphite CFRE *
Polymers have... Silicone
PVC A ramid fibers
AFRE *
PET
• low packing density 1 PC
HDPE, PS
(often amorphous) PP, LDPE

• lighter elements (C,H,O)

0.5
Wood
0.4
Composites have... 0.3
• intermediate values
32
 Single vs Polycrystals
Single Crystals E (diagonal) = 273 GPa

Properties vary with

direction: anisotropic.
Example: the modulus
of elasticity (E) in BCC iron
E (edge) = 125 GPa
Polycrystals
Properties may/may not 200 μm
vary with direction
If grains are randomly
oriented: isotropic
(Epoly iron = 210 GPa)

If grains are textured,

anisotropic
33
 Polycrystals
Most engineering materials are polycrystals.
Anisotropic

1 mm

Isotropic
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 typically range from 1 nm to 2 cm

(i.e., from a few to millions of atomic layers)
34
 Crystals as Building Blocks

Some engineering applications require single crystals:

Diamond single
crystals for abrasives Turbine blades

Properties of crystalline materials

are often related to crystal structure.

Quartz fractures more easily

along some crystal planes than
others.

35
 Polymorphism

Two or more distinct crystal structures for the same

material (allotropy/polymorphism)
Iron

liquid
1538C
Iron, Titanium, BCC δ Fe
Carbon 1394C
FCC γ Fe
912C
BCC α-Fe

36
 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

We shall only be dealing with the

cubic system

Face Centred Cubic (FCC)

Body Centred Cubic (BCC) 37
VMSE Screenshot – [101] Direction

38
VMSE Screenshot – Crystallographic Planes

Additional practice on indexing crystallographic planes

39
VMSE Screenshot – Atomic Packing –
(111) Plane for BCC

40
 Summary

Atoms may assemble into crystalline or amorphous structures

Common metallic crystal structures are FCC, BCC

We can predict the density of a material, provided we

know the atomic weight, atomic radius, and crystal
geometry (e.g., FCC, BCC).

Crystallographic points, directions and planes are

specified in terms of indexing schemes

41
 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).

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 Home Assignments

Study Tutorial Videos

FCC Unit Cell Calculations, p. 55
BCC Unit Cell Calculations, p. 56

Study Example problems

3.1, 3.2, 3.4

Study Figures
3.12, 3.13, 3.15, 3.18, 3.20

Do Problems
3.2, 3.7, 3.9, 3.22