Chapter 3

The Structure of Crystalline Solids

Outline

• Crystalline versus amorphous structures

• Crystal structure
- Unit cell
- Lattice
- Types of crystal structures
- Coordination number
- close pack directions
- Atomic packing factor
• Crystal systems
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Motivation:
In addition to atomic bonding, the physical properties of
materials depend on the way atoms are packed together (or
arranged). Many of the properties of materials (especially
mechanical) are determined by the arrangement of the constituent
atoms.

This arrangement is called the material’s crystal structure.

• An important distinction…

1) Atomic structure (subatomic level) relates to the number of

protons and neutrons in the nucleus of an atom, as well as the
number and probability distributions of the constituent electrons.

2) On the other hand, crystal structure (crystal level) pertains to the

arrangement of atoms in the crystalline solid material.
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• The crystal structure is explained using the hard sphere model (in
which nearest neighbor atoms “touch” each other)…

“atoms are thought of as solid spheres with spheres

touching each other”

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Now place an atom at each corner.
This represents the “hard sphere”
model
of a …………………. Crystal system

• Atoms “touch” along the crystal axes

• These directions are referred to as “close
packed” in the simple cubic system

not many examples of simple cubic systems in nature, except for Po

(Polonium).

The above diagram represents a simple cubic ………..

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Terms Employed: BCC Lattice

Lattice: Three dimensional array of points coinciding

with atom positions (or hard spheres centers)

What is Unit Cell?

- A unit cell is the smallest entity that exhibits the chemical and
physical properties of the material.

- Unit cells are the most elementary arrangement of atoms

(building block) which can generate the entire crystal structure upon
application of suitable translation, rotation, mirror, or inversion
operations.

Unit cells for most crystal structures are parallelepiped or prisms

having three sets of parallel faces
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Definition:

the length of each unit cell axis is called a lattice parameter

– In simple cubic systems, all three orthogonal lattice parameters are

equal

– Lattice parameters are typically on the order of a few Angstroms (1x

10-10 m) or a few tenths of a nanometer (1 X 10-9 m)

The other lattice parameters are the angles (three angles).

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 METALLIC CRYSTALS
• 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: Three of the most

common crystal structures found in metals are:
– Body centered cubic (BCC)
– Face centered cubic (FCC)
– Hexagonal close packed (HCP)

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Coordination Number, close pack directions and APF
• Three important characteristics of crystal structures are:
1. Coordination Number
2. Atomic Packing Factor
3. Close pack directions
(1) Coordination Number: Number of nearest neighbor or
touching atoms
(2) Atomic Packing Factor (APF): Volume of atoms in a unit cell
divided by the total unit cell volume
(3) The close packed directions are the directions at which the
atoms are closest to one another without a gap. important to
know which slip direction are there in the crystal structures
* To calculate APF the following additional information is also
required:
“Number of atoms per unit cell”
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How many atoms does the simple cubic unit cell contain?

You should be able to convince yourself that a simple cubic

structure contains … one…atom/unit cell.

(Remember, a part of each atom is shared by another unit cell!)

• The number of atoms/unit cell is an important quantity and

determines many physical properties.

• In general (for all the crystal types) the number of atoms/unit cell,
N, is given by:

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Note: The energy required for slip to occur in close pack
directions are much smaller than that in the non-close pack
directions (imagine moving without wheels)

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 SIMPLE CUBIC STRUCTURE (SC)

Unit cell Lattice

• Coordination # = 6
(# nearest neighbors)
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 Simple Cubic Structure (Only for Illustration)
• Rare in metals due to poor packing
• Atomic Packing Factor (APF) for a simple cubic structure = 0.52
• Coordination Number = 6
• Close Packed Directions are Cube Edges
Volume of atoms in unit cell*
APF =
a Volume of unit cell

R=0.5a *assume hard spheres

volume
close-packed directions = a atoms
4 atom
contains 8 x 1/8 = unit cell 1 (0.5a)3
1 atom/unit cell 3
APF =
a3 volume
unit cell
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 BODY CENTERED CUBIC STRUCTURE (BCC)
• Atoms located at all 8 corners and a single atom at the cube center
• Center and corner atoms touch each other but the corner atoms don’t

Notice that in the BCC structure,

atoms touch along the body
diagonals. These are the close-
packed directions in the body
centered cubic structure.
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 Body Centered Cubic Structure (BCC)
• APF for a body-centered cubic structure = 0.68
• Coordination Number = 8
• Close Packed Directions are Cube Diagonals

Close-packed directions:
length = 4R
= 3a
Example:
R Calculate the APF for a BCC unit cell:
a
atoms volume
4 3
Unit cell contains unit cell 2 ( 3a/4)
3 atom
1 + 8 x 1/8 = 2 atoms/unit cell APF =
volume
a3
unit cell
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 FACE CENTERED CUBIC STRUCTURE (FCC)
• Atoms located at each of the corners and center of all cube faces
• The atom touch one another across the face diagonal

Close-packed directions
in FCC metals are along
face diagonals

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 Face Centered Cubic Structure (FCC)
• APF for a face-centered cubic structure = 0.74
(Maximum possible packing for spheres all having same diameter)

• Coordination Number = 12 (top face atom)

• Close Packed Directions are Face Diagonals

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

atoms volume
a 4 3
unit cell 4 ( 2a/4)
3 atom
Unit cell contains: APF =
volume
6 x 1/2 + 8 x 1/8 a3
unit cell
= 4 atoms/unit cell
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HEXAGONAL CLOSE-PACKED STRUCTURE (HCP)
• Not a cube but hexagonal structure
• Top and bottom face of the unit cell consist of 6 atoms forming a
hexagon with an atom in center.
• Another plane provide 3 additional atoms and is situated between top
and bottom
• Coordination No and APF same as FCC (12 and 0.74 respectively)

# atoms/unit cell = (1/6)*12 (corner

atoms) + (1/2)*2 (center face
atoms) + 3 (interior atoms) = 6

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 Hexagonal Closed Packed Structure (HCP)

• ABAB... Stacking Sequence

A sites Top layer

B sites Middle layer
A sites Bottom layer

3D Projection 2D Projection

• Coordination Number = 12
• APF = 0.74
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 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 A

B
C

a
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 FCC STACKING SEQUENCE
• ABCABC... Stacking Sequence

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 THEORETICAL DENSITY, 

A knowledge of crystal structure permits calculation of

theoretical density  Through the relationship:

# atoms/unit cell Atomic weight (g/mol)

 nA
Volume/unit cell VcNA Avogadro's number
(cm3/unit cell) (6.023 x 10 23 atoms/mol)

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 Example Problem 3.3
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 = 10-7 m)
• Compute its theoretical density and compare the answer
with its measured density:

Vc = a3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10-23cm3

Result: theoretical Cu = 8.89 g/cm3

Compare to actual: Cu = 8.94 g/cm3

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 Characteristics of Selected Elements at 20C
At. Weight Density Crystal Atomic radius
Element Symbol (amu) (g/cm3) 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 ------
Bromine Br 79.90 ------ ------ ------
Cadmium Cd 112.41 8.65 HCP 0.149
Calcium Ca 40.08 1.55 FCC 0.197
Carbon C 12.011 2.25 Hex 0.071
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 ------ ------ ------ 15 24
 DENSITIES OF MATERIAL CLASSES
metals> ceramics> polymers
Graphite/
Metals/ Composites/
Why? Alloys
Ceramics/ Polymers
Semicond
fibers
Metals have... 30
Based on data in Table B1, Callister
Platinum
• close-packing 20 Gold, W
*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
Tantalum
(metallic bonding) Epoxy composites (values based on
60% volume fraction of aligned fibers
• large atomic mass 10 Silver, Mo
Cu,Ni
in an epoxy matrix).
Steels

 (g/cm3)
Ceramics have... Tin, Zinc
Zirconia
• less dense packing 5
Titanium
4 Al oxide
Diamond
(covalent bonding) 3 Si nitride
Aluminum Glass-soda Glass fibers
• often lighter elements Concrete
Silicon PTFE
2 GFRE*
Magnesium Carbon fibers
Polymers have... Graphite
Silicone CFRE*
Aramid fibers
PVC AFRE*
• poor packing 1
PET
PC
HDPE, PS
(often amorphous) PP, LDPE

• lighter elements (C,H,O) 0.5

Wood
Composites have... 0.4
0.3
• intermediate values 25
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 Polymorphism and Allotropy
• Presence of more than one Crystal Structure in a
given material (Allotropy term used for elemental
solids)
• The equilibrium crystal structure present depend
on Temperature and Pressure
• Example:
– Carbon:
• Graphite at atmospheric conditions
• Diamond at high pressures
– Iron:
• BCC at room temperature
• FCC at 912 C

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 Single Crystalline Vs. Polycrystalline Materials
• Single Crystals:
– For a crystalline solid, when the periodic and repeated 3-
dimensional arrangements of atoms is perfect or extends
throughout the entirety of the specimen without interruption
the result is a single crystal
– Required complex growing techniques (expensive)
– Used in electronic microcircuits employing single crystals
of Silicon

• Polycrystalline:
– Collection of many small crystal or grains
– Small crystals or nuclei grow at several locations and meet
at grain boundaries

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POLYCRYSTALS

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Single Crystalline Vs. Poly-Crystalline Materials (Contd)

• Single Crystals:
– Some engineering applications require
single crystals
– E.g: Turbine Blades and diamond
Single crystals for abrasives

• Poly-Crystalline:
– Most engineering materials are polycrystalline
– Also called multi-grain systems with each “grain” a
single crystal
– Grain or crystal size typically range form 1 nm to 2 cm
(i.e. from a few to millions of atomic layers)
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 Anisotropy Vs. Isotropy
• Anisotropy: E (diagonal) = 273 GPa
– The physical properties vary with direction
– The properties of single crystals depend on
crystallographic direction
– Example: the modulus of elasticity E (for single
crystal of BCC iron values are shown),
electrical conductivity and index of refraction E (edge) = 125 GPa

200 m
• Isotropy:
– Properties independent of direction
– For many polycrystalline materials the grains
are randomly placed so even each grain may be
anisotropic, the aggregate behave as: isotropic
– Sometimes grains in polycrystalline material
have preferred crystallographic orientation and
material is said to have a “texture”: anisotropic
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 Summary
• Atoms may assemble into crystalline or
amorphous 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)

• Material properties generally vary with single crystal

orientation (i.e., they are anisotropic), but properties
are generally non-directional (i.e., they are isotropic)
in polycrystals with randomly oriented grains.

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