STRUCTURE OF MATERIALS

COURSE OUTCOME
Identify the structure of various types of
engineering materials, explain the methods to
determine their properties and apply the
knowledge of materials in selection of
material for construction of process
equipment
 ATOMIC STRUCTURE

Basic atomic calculations (MW, moles, quantity of atoms)

Coordination number (CN) and atomic radius

Relationship between CN and atomic radius

 THE STRUCTURE OF ATOMS

Some of the important properties of solid materials

depend on geometrical atomic arrangements, and
the interactions that exist among constituent atoms
or molecules.

Each atom consists of 3 basic subparticles: a very

small nucleus composed of protons and neutrons,
which is encircled by moving electrons.
Atomic structure: The Bohr Model

Schematic representation of the Bohr atom

 Structure of Atoms
ATOM
Basic Unit of a material
Neutrally Charged
Diameter : 10 10 m.

Nucleus Electron Cloud

Diameter : 10 14 m Mass : 9.109 x 10 28 g
Accounts for almost all mass Charge : -1.602 x 10 9 C
Positive Charge

Proton
Mass : 1.673 x 10 24 g Neutron
Charge : 1.602 x 10 19 C Mass : 1.675 x 10 24 g
Neutral Charge
Viewing of an atom
Periodic Table
 Fundamental Concepts

Mass
Number
23 Element
Atomic 11 Na symbol
Number
Atomic number of protons
number
in the nucleus

the sum of number

Mass
number
of protons
and neutrons

atoms with the same

isotopes number of protons
but different
number of neutrons.
 Isotopes

23 24
11 Na 11 Na
 Atomic Number and Atomic Mass

Atomic Number = Number of Protons in the nucleus

Unique to an element
Example :- Hydrogen = 1, Uranium = 92
Relative atomic mass = Mass in grams of 6.203 x 1023 Atoms.
( Avogadro Number)
The relative atomic mass of elements from 1-105 are located below the
atomic symbols in the periodic table of the elements
Carbon 12 atom is the reference mass for atomic masses.
One gram mole = Gram atomic mass of an element.
Example :-

One gram 6.023 x 1023

26.98 Carbon
Mole of
Grams of mass Atoms
Aluminium
 Atomic Mass Unit (amu)
1 amu is defined as of the atomic mass of the
most common isotope of carbon, carbon 12,
which has the mass of 12 amu.

Primary bonds

Atomic Bonding

Secondary bonds

Molecule is a group of atoms that are bonded together by

strong primary bonds.
Elements are made up of small particles
known as atoms.

The forces that hold atoms together are

known as chemical bonds.

Molecule is a group of atoms that are

bonded together by strong primary bonds.
Mole = the number equal to the number of carbon
atoms in exactly 12 grams of pure 12C

Avogadros Number (6.022 X 1023) is defined as the

number of atoms in exactly 12 grams of 12C.

This also means that a 12.01-gram sample of

natural carbon contains 6.022 x 1023 atoms
(mixture of 12C, 13C and 14C)
 Example 1

a) What is the mass in grams of one atom of copper?

6.022 x 1023 atoms weiged 63.54 gm
Therefore, 1 atom of copper is (63.54/6.023 X 10 23 ) gm = 1.055 x 10-22 gm

a) How many copper atoms are in 1 g of copper?

OR 63.54 gm of Cu contains 6.022 x 1023 atoms
Therefore, 1 g of Cu contains 9.477 x 1021 atoms

Given: Atomic mass of copper is 63.54 g/mol.

 Example 2

a) How many moles in a 20 gram sample of Iron (Fe)?

1 mole of Fe weighs 55.85 gm, therefore in 20gm.. 20/55.85 = 0.358 moles

a) How many atoms are there in 30g of aluminium

oxide powder?
26.98 gm of aluminium contains 6.022 x 1023 atoms

Therefore, in 30 g Al contains 6.022 x 1023 /26.98 x 30 = 6.69 x 1023 atoms

 Example 4

A 100 gram alloy of nickel and copper consists

of 75 wt% Cu and 25 wt% Ni. What are
percentage of Cu and Ni Atoms in this alloy?

Given:- 75g Cu
Atomic Weight 63.55
25g Ni
Atomic Weight 58.69
 Coordination number

Coordination number (CN) is the

number of adjacent ions or atoms
surrounding a reference ion or atom

The CN is calculated by counting the

maximum number of atom in close
contact or in contact with the reference
atom.
Figure 1.1: Arrangement of four atoms
surrounding reference atom
Calculation of radius ratio, r/R.

Calculation of radius ratio,

.
r = radius of the reference atom
R = radius of the surrounding atom

AD = R + r
cos 30o = AE R
0.866
AD R r
R = 0.866(R+r) = 0.866R + 0.866r
0.866r = R 0.866R = R(0.134)
r/R = 0.155
( can have 3 other atoms in coordination)
Relationship between CN and atomic radii.

r/R
The coordination
number of the central
(red) atom in each of
the polyatomic ions
above is equal to the
number of blue atoms
that surround it, and
corresponds to a
regular geometric
shape.
 Atomic and Molecular Bonds

Ionic bonds :- Strong atomic bonds due to transfer of

electrons
Covalent bonds :- Large interactive force due to sharing of
electrons
Metallic bonds :- Non-directional bonds formed by sharing of
electrons
Permanent Dipole bonds :- Weak intermolecular bonds due
to attraction between the ends of permanent dipoles.
Fluctuating Dipole bonds :- Very weak electric dipole bonds
due to asymmetric distribution of electron densities.
 Example 3
An intermetallic compound has the general chemical
formula NixAly, where x and y are simple integers, and
consists of 42.05 wt% nickel and 57.95 wt% aluminium.
What is the simplest formula of this nickel aluminide?
Basis: 100 gm of the compound

Nickle = 42.05/58.69 = 0.716 mol

Al= 57.95/26.98 = 2.15 mol

Therefore, we can write. Nio.716Al2.15 OR NiAl3

 SECTION 1

ATOMIC ORDER IN SOLIDS

 PURPOSE
To look specifically at the atomic
arrangements in a few of the more simple
structures such as bcc, fcc and hcp.
Establish the credibility of their existence
through density calculations
 Crystallinity
All metals, some fraction of ceramics and
certain polymers crystallize when they solidify
The atoms arrange themselves into an
ordered, repeating, 3D pattern, which called
crystals
An imaginary network of lines, with atoms at
intersection of lines, representing the arrangement of
atoms is called space lattice.

Unit cell is that block of

atoms which repeats itself
to form space lattice.

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 Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
7 crystal systems: Cubic,
tetragonal, orthorhombic,
Rhombohedral, hexagonal,
monoclinic and triclinic
*to cover on CUBIC only
The size and shape of the unit cell
can be described by three lattice
vectors; a, b, and c
The axial length of a, b, and c
are the lattice constants
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 7 different types of unit cells necessary to
create all point lattices.

August Bravais (1811-1863) derived 14

possible unit cells to describe all possible
lattice networks. *We learn 3 only. See Fig 3.2
Smith

In the cubic system, the 3 types of unit cells

are
Simple Cubic
Body Centered (BCC)
Face Centered (FCC)
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The 14 Bravais Lattices

35
 7 Types of Unit Cells
Cubic Unit Cell
a=b=c
= = = 900
Simple Body Centered

Figure 3.2

Face centered

Tetragonal
a =b c
= = = 900
Simple Body Centered

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 Orthorhombic
a b c
= = = 900

Simple Base Centered

Body
Face Centered
Centered

Rhombohedral
a =b = c
= = 900 Simple

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 Hexagonal
a b c
= = = 900
Simple

Monoclinic
a b c
= = = 900

Simple

Triclinic Figure 3.2

a b c
= = = 900
Simple
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 PRINCIPAL METALLIC CRYSTAL
STRUCTURES

90% of the metals have either: Body Centered Cubic

(BCC), Face Centered Cubic (FCC) or Hexagonal Close
Packed (HCP) crystal structure.
**HCP is denser version of simple hexagonal crystal
structure.

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 Simple Cubic

Number of atoms in a unit cell?

1/8th of an atom are at the cube corners
= 8 corners (1/8 atom)
= 1

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 Atomic Packing Factor (APF)

Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres

volume
atoms atom
4
a unit cell 1 p (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions unit cell
contains 8 x 1/8 =
1 atom/unit cell **APF for a simple cubic structure = 0.52
Adapted from Fig. 3.23,
Callister 7e.
41
 ATOMIC PACKING FACTOR (APF)
It is the fraction of solid sphere volume in a
unit cell, assuming the atomic hard sphere
model.
It is the maximum packing possible for
spheres all having the same diameter.

Volume of atoms in unit cell, Va

Atomic Packing Factor =
Volume of unit cell, Vc

**The higher the APF, Crystal structure is more packed.

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 a 3
Vc a 2 R
3 SIMPLE
3 CUBIC

Va
APF 0.52
Vc
where

Va 1 4 pR 3 This means that SC 52%

packed with 1 atom.
3
Vc a 2 R
3 3 (48% empty space).

It is not a closed-packed
Va structure.
APF 0.52
V 43
 Body Centered Cubic Structure (BCC)
Represented as one-eighth of atom at each corner of
cube and one at the center of cube.

Adapted from Fig. 3.2,

(Courtesy P.M. Anderson) Callister 7e.

--Note: All atoms are identical; the

center atom is shaded differently 2 atoms/unit cell: 1 center + (8 corners x 1/8)
only for ease of viewing.
44
Body Centered Cubic (BCC) Crystal
Structure

ex: Cr, W, Fe (), Tantalum, Molybdenum

45
 Each unit cell has eight 1/8
atom at corners and 1
full atom at the center.
Therefore each unit cell has
(8x1/8 ) + 1 = 2 atoms
Atoms contact each
other at cube diagonal

Relationship between cube side length (a)

and atomic radius (R) :

Therefore, lattice 4R
constant, a =
3
46
 Atomic Packing Factor: BCC

3a

2a

Close-packed directions:
R length = 4R = 3 a
Adapted from
Fig. 3.2(a), Callister 7e.
a
atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell 47
 Example Question: BCC
Calculate the APF for the BCC unit cell, assuming the atoms to be hard
spheres

Va 2 pR 3
4 This means that BCC 68%
packed with 2 atoms.
3
3 (32% empty space).
4R
Vc a 3

3 BCC is not a closed-
packed structure.
APF 0.68
APF for a body-centered cubic structure = 0.68
WHAT DOES THIS MEAN?

48
 Example Problem
Iron (Fe) at 20C is a BCC with atoms of atomic radius
0.124 nm. Determine the lattice constant, a of the
cube edge of the iron unit cell.

4R=3 a

a = 4R/3

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 Solution

Solution:

4R
a = = 0.2864 nm
3

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Table 3.2 (Smith) Selected metals which have the BCC crystal structure
at room temperature (20C) and their lattice constants and atomic
radii

Metal Lattice constant a, nm *Atomic radii R, nm

Chromium 0.289 0.125
Iron 0.287 0.124
Molybdenum 0.315 0.136
Potassium 0.533 0.231
Sodium 0.429 0.186
Tantalum 0.330 0.143
Tungsten 0.316 0.137
Vanadium 0.304 0.132

*Calculated from lattice constant using equation 4R = 3 a

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 Face Centered Cubic (FCC)
Crystal Structure
FCC structure is represented as one atom each at the corner
of cube and at the center of each cube face.

Adapted from Fig. 3.1, Callister 7e.

(Courtesy P.M. Anderson)

--Note: All atoms are identical; the face-centered atoms are shaded differently for
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ease of viewing.
 Face Centered Cubic Structure (FCC)
Atoms touch each other along face diagonals.
ex: Al, Cu, Au, Pb, Ni, Pt, Ag

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

53
Face Centered Cubic (FCC) Crystal
Structure

Each unit cell has eight 1/8th

atom at corners and six
atoms at the center of six faces.
Therefore each unit cell has:

(8 x 1/8)+ (6 x ) = 4 atoms/unit cell

54
 Relationship between cube edge
length and atomic radius for FCC
a2 + a2 = 2 a

4R
a
2

55
 Atomic Packing Factor: FCC
Close-packed directions:
length = 4R = 2 a Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell

atoms volume
4
2a unit cell 4 p ( 2a/4) 3
3 atom
APF =
volume
a3
a unit cell
Adapted from
Fig. 3.1(a),
Callister 7e.
56
 Face Centered Cubic
4 3
Va (4) pR
3
3
4R
Vc a
3

2
APF 0.74
APF for a FCC structure = 0.74
(maximum achievable APF)
57
 APF of FCC
APF = 0.74, which is greater than BCC (0.68)
This means that 74% of the FCC unit cell
volume is filled by 4 atoms.
Atoms in FCC are packed as close together as
possible.
It is a close-packed structure.
26% is empty space.

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 Hexagonal Close-Packed Structure (HCP)

The HCP structure is represented as an atom at

each of 12 corners of a hexagonal prism, 2 atoms
at top and bottom face and 3 atoms in between
top and bottom face.

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 Hexagonal Close-Packed Structure (HCP)
ABA... Stacking Sequence
3D Projection 2D Projection

A sites Top layer

c Middle layer
B sites

A sites Bottom layer

a Adapted from Fig. 3.3(a),
Callister 7e.

6 atoms/unit cell
APF = 0.74
ex: Cd, Mg, Ti, Zn

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 Hexagonal Close-Packed Structure (HCP)

Each unit cell has six 1/6th

atoms at each of top and
bottom layer, two half atoms at
top and bottom layer and 3 full
atoms at the middle layer.
Therefore each HCP unit cell
has:

(2 x 6 x 1/6) + (2 x ) + 3 = 6 atoms
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 Densities of Material Classes
In general Graphite/
rmetals > rceramics > rpolymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum
Based on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
often large atomic masses Tin, Zinc
Zirconia

r (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
less dense packing 3
Diamond
Si nitride
Aluminum Glass -soda
often lighter elements Concrete
Silicon PTFE
Glass fibers
GFRE*
2 Carbon fibers
Polymers have... Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC
low packing density PET
PC
AFRE*
1 HDPE, PS
(often amorphous) PP, LDPE
lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

intermediate values 0.3

Data from Table B1, Callister 7e.
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 Density Calculation

r
massunitcell n MW
volumeunitcell
Vc N A
Where:
n = number of atoms per unit cell
MW = molecular/atomic weight (g/mol)
Vc = Volume of a unit cell (m3)
NA = Avogadros No. (6.022 X 1023)
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 Theoretical Density, r
Mass of Atoms in Unit Cell
Density = r =
Total Volume of Unit Cell

nA
r =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.023 x 1023 atoms/mol

64
 Theoretical Density, r

Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2

R a = 4R/ 3 = 0.2887 nm
a
atoms
g
unit cell 2 52.00 rtheoretical = 7.18 g/cm3
mol
r= ractual = 7.19 g/cm3
a3 6.023 x 1023
volume atoms
unit cell mol 65
 Volume Density
Volume density of metal = rv =
Mass/Unit cell
Volume/Unit cell

Example:- Copper (FCC) has atomic mass of 63.54

g/mol and atomic radius of 0.1278 nm. Determine
volume density of copper.

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 Volume Density
Volume density of metal = rv =
Mass/Unit cell
Volume/Unit cell

Example:- Copper (FCC) has atomic mass of 63.54

g/mol and atomic radius of 0.1278 nm.

67
 Polymorphism and Allotropy
Some materials may exist in more than one
crystal structure (FCC,BCC or simple cubic),
this phenomenon is called polymorphism.
If the material is an elemental solid, it is called
allotropy.
An example of allotropy is carbon, which can
exist as diamond (at high pressure) and
graphite (at ambient condition)

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 Polymorphism or Allotropy
Metals exist in more than one crystalline form. This is caller
polymorphism or allotropy.
Temperature and pressure leads to change in crystalline
forms.
Example:- Titanium, Iron, Cobalt
- Iron exists in both BCC and FCC form depending on the
temperature. Liquid
Iron

-2730C 9120C 13940C 15390C

Iron Iron Iron

BCC FCC BCC
69
3-33
 Tutorial on crystal structure
1. Molybdenum has a BCC crystal structure, an atomic
radius of 0.1363 nm, and an atomic weight of 95.94
g/mol. Determine its density.
2. Calculate the radius of a palladium atom, given that
Pd has an FCC crystal structure, a density of 12.0
g/cm3 , and an atomic weight of 106.4 g/mol.
3. Calculate the radius of a tantalum atom, given that
Ta has a BCC crystal structure, a density of 16.6
g/cm3 , and an atomic weight of 180.9 g/mol

70
4. Below are listed the atomic weight,
density, and atomic radius for three
hypothetical alloy. For each determine
whether its crystal structure is FCC, BCC
or simple cubic. Justify your determination.

Alloy Atomic weight Density (g/cm3) Atomic Radius

(g/mol) (nm)

A 43.1 6.40 0.122

B 184.4 12.30 0.146

C 91.6 9.60 0.137

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 Tutorial on electronic configuration of elements

1. Write electronic configuration of metals, gases, non metallic

elements

2. From these configurations, can you differentiate them ? Give

examples

3. What do you know about ionic bonding, metallic bonding, covalent

bondings, Wan Der Waal forces and hydrogen bonding? Illustrate
and differentiate with diagrams and give examples.

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