Chapter 3

The Structure of Crystalline Solids

Outline

Crystalline versus amorphous structures

Crystal structure
- Unit cell
- Coordination number
- 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 materials crystal structure.

An important distinction

1) Atomic structure (atomic 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. 2
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We need a way to specify crystallographic directions and planes.

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

We cant specify directions or

planes without knowing
what the reference system is.
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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 center ed cubic (BCC)
Face center ed 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 oneatom/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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 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

=a

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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 dont

Notice that in the BCC

str ucture, atoms touch along
the body diagonals. These are
the close-packed directions in
the body centered cubic
str ucture. 14
 Body Centered Cubic Structure (BCC)
APF for a body-centered cubic structure = 0.68
Coordination Number = 8
Close Packed Directions are Cube Diagonals

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

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 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

B sites

A sites

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
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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:

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 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 ------ ------ 15 23
 DENSITIES OF MATERIAL CLASSES
metals> ceramics> polymers

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...
intermediate values 24
 Crystallographic points, Directions &
Planes
Now that we know how atoms arrange themselves to form
crystals, we need a way to identify dir ections and planes of
Atoms

Why?

1) Deformation under loading (slip) occurs on certain crystalline

planes and in certain crystallographic directions. Before we can
predict how materials fail, we need to know what modes of
failure are more likely to occur.

2) Other properties of materials (electrical conductivity, thermal

conductivity, elastic modulus) can vary in a crystal with orientation.

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Crystallographic Points, Directions and Planes

Elaborate Labeling Conventions Exists for:

Point Coordinates q r s

Crystallographic Directions [u v w]

Crystallographic Planes (h k l) Miller Indices

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27
 Crystal Systems

Unit cell geometry defined by six

parameters:
3 edges a, b & c
Lattice Parameters
3 interaxial angles , &

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 Point coordinates

Point position specified in terms of its

coordinates as fractional multiples of the
unit cell edge lengths (See examples: 3.5 in
the book).

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General Rules for Lattice Directions, Planes & Miller Indices

Miller indices are used to express lattice planes and

directions
x, y, z are the axes (on arbitrarily positioned origin)
in some crystal systems these are not mutually
Perpendicular
a, b, c are lattice parameters (length of unit cell along a
side)
h, k, l are the Miller indices for planes and directions
expressed as planes: (hkl) and directions: [hkl]
Conventions for naming:
There are NO COMMAS between numbers
Negative values are expressed
with a bar over the number, Example: -2 is expressed 2 30
Miller Indices for Directions

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Example(1): Example(2):

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 Miller Indices for Planes

Note: We always have [111] (111) in cubic crystals

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Close Pack Planes and Directions

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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 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:
The physical pr oper ties var y with dir ection
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
200 m
Isotropy:
Pr oper ties independent of dir ection
For many polycrystalline materials the grains
are randomly placed so even each grain may be
anisotropic, the aggregate behave as: isotr opic
Sometimes grains in polycrystalline material
have preferred crystallographic orientation and
material is said to have a texture: anisotr opic
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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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