Chapter 3: The Structure of Crystalline Solids

• In addition to atomic bonding, the physical and

mechanical properties of materials depend on
the way atoms are packed (or arranged)

• Level of Structure: 1. Atomic Bonding

2. Packing of Atoms:
Crystalline Vs. Non-Crystalline

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Chapter 3: The Structure of Crystalline Solids

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?

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Crystalline Vs. Non-Crystalline Structures
• Crystalline Materials:
– Atoms are arranged in periodic (repetitive) 3-dimensional
pattern over large atomic distances

Long range order exist

– Examples: All Metals, Many Ceramics, and some
Polymers

• Non-Crystalline Materials:
– Amorphous Non-Crystalline
– No long range order exist, i.e., no periodic packing
– Occurs for: - Complex Structures
- Rapid Cooling
– Examples: Glasses
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• Crystal Structure are explained by:
“Atomic Hard Sphere Model”
In this model atoms are thought of as solid spheres with
spheres touching each other
• Terms Employed:
– Lattice: Three dimensional array of points coinciding with atom
positions (or hard spheres centers)

– Unit cell:
• Smallest repeat entities or pattern are called Unit cells

• Unit cells are the basic structural unit or building block of the
crystal structure defining the crystal structure

• Unit cells for most crystal structures are parallelepiped or

prisms having three sets of parallel faces

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 The 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 and APF
• Two important characteristics of crystal structures are:
(1) Coordination Number
(2) Atomic Packing Factor
• (1) Coordination Number: Number of nearest neighbor or
touching atoms to any atom in a unit cell
• (2) Atomic Packing Factor (APF): Volume of atoms in a
unit cell divided by the Total unit cell volume
• To calculate APF following additional information is also
required:
(3) Number of atoms per unit cell
(4) The close packed directions
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SIMPLE CUBIC STRUCTURE (SC) (only for Illustration)

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

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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

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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

atoms volume
R 4 3
a unit cell 2 p ( 3a/4)
3 atom
APF =
volume
Unit cell contains a3
1 + 8 x 1/8 unit cell
= 2 atoms/unit cell 11
 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

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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
• 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)

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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

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 THEORETICAL DENSITY, r

• A knowledge of crystal structure permits calculation of

theoretical density r Through the relationship:

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

r= 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 cm)
• Compute its theoretical density and compare the answer
with its measured density:

Result: theoretical rCu = 8.89 g/cm3

Compare to actual: rCu = 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 19
 Densities of Materials Classes
rmetals> rceramics> rpolymers
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
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 Polymorphism and Allotropy
• Presence of more than one Crystal Structure in a
given materials (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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 Crystal Systems

• Unit cell geometry defined by six

parameters:
– 3 edges a, b & c Lattice Parameters
– 3 interaxial angles ,  & 
• Seven Crystal Systems exists:
Cubic, Tetragonal, Hexagonal, Orthorhombic,
Rhombohedral, Monoclinic, and Triclinic
• FCC and BCC  Cubic
HCP  Hexagonal
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23
 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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 Section 3.8 Point Coordinates
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2 ½½½

000
y
a b
Point coordinates for unit cell
x  corner are 111
z 2c

Translation: integer multiple of
  lattice constants  identical
b y position in another unit cell
b
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 Crystallographic Directions
z Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

x [uvw]

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a negative
index
families of directions <uvw>
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 Crystallographic Planes
• Miller Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of fractions &
common multiples. All parallel planes have same
Miller indices.

• Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)

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 Crystallographic Planes
z
example a b c
1. Intercepts 1 1 
c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
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 Crystallographic Planes

Adapted from Fig. 3.9, Callister 7e.

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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

• 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 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
200 mm
• 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”: anisotropy
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X-RAYS TO CONFIRM CRYSTAL STRUCTURE

• Incoming X-rays diffract from crystal planes.

Adapted from Fig.

3.2W, Callister 6e.

• Measurement of:
Critical angles, qc,
for X-rays provide
atomic spacing, d.
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 X-Ray Diffraction Pattern
z z z
c c c

y (110) y y
a b a b a b
Intensity (relative)

x x x (211)

(200)

Diffraction angle 2q

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.20, Callister 5e.

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 Non-Crystalline (Amorphous) Materials
• Amorphous means without form or
supercooled liquids (lack of symmetric &
regular arrangements of atoms)

• Whether crystalline or amorphous solid forms crystalline SiO2

depends on the ease with which a random
atomic structure in the liquid can transform to
an ordered state during solidification

• Amorphous structure occurs for complex

structure and rapid cooling
noncrystalline SiO2

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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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 Home Work # 2
ME 207: Engineering Metallurgy

Problem 1: For a Na+ and Cl- ion pair, attractive and repulsive energies EA and ER,
respectively, depend on the distance between the ions r, according to:
EA =-1.436/r and ER=7.32 x 10-6/r8.
For these expressions, energies are expressed in electron volts per
Na+ and Cl- pair, and r is the distance in nanometers. The net energy
EN is just the sum of the two expressions above.

(a) Superimpose on a single plot EN, ER and EA versus r up to 1.0 nm

(b) On the basis of this plot determine (i) the equilibrium spacing r o
between Na+ and Cl- ions, and (ii) the magnitude of bond
energies Eo between the two ions. (Text Problem 2.14)

Problem 2: The table below gives the melting points of five different materials:

Material Melting Point (oC)

Mild Steel 1530
Low Density Polyethylene 100
Nylon 66 265
Magnesium chloride 714
Argon -189

Identify the bonding system(s) operating in each case and explain why
the range of melting points shown above is so wide.

Problem 3: (a) If the atomic radius of Aluminum is 0.143 nm, calculate the volume
of its unit cell in cubic meters. (Text Problem 3.3)

(b) Iron has BCC crystal structure, an atomic radius of 0.124 nm, and
an atomic weight if 55.85 g/mol. Compute and compare its theoretical
density with the experimental value. (Text Problem 3.8)
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Problem 4: (a) Calculate the radius of a Vanadium atom, given that V has a BCC
crystal structure, a density of 5.96 g/cm3, and an atomic weight of
50.9 g/mol. (Text Problem 3.10)

(b) Niobium has an atomic radius of 0.143 nm and a density of 8.57

g/cm3. Determine whether it has an FCC or BCC crystal structure.
(Text Problem 3.14)

For practice also Try other related Text Problems at the end of Chapter 3
(such as 3.4, 3.6, and 3.11)

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