CHAPTER 1

MATERIAL SCIENCE
 Topics
1.1 Atomic structure and crystal structure

1.2 Solidification

1.3 Crystalline imperfections in solid

1.4 Phase diagram

Course
Outcomes

Evaluate the principles of material properties in

02 solving problems related to process equipment
(C4).
e-book:

Chapter 2
Chapter 3
Chapter 4
Chapter 9
• 1.1 Atomic structure
• 1.2 Crystal structure
Understanding
materials….
Properties
“Materials Science” “Materials Engineering”

Structure Processing

• Electronic level (subatomic)

• Atomic (molecular level, chemical composition)
• Crystal (arrangement of atoms or ions wrt one another)
• Microstructure (can study with microscopes)
• Macrostructure (can see with naked eye)
 1.1 Atomic
Structure
What is the structure of an atom?
Protons, neutrons and electrons are not evenly distributed in
an atom.
The protons and neutrons exist
in a dense core at the centre
of the atom. This is called the
nucleus.
The electrons are spread out
around the edge of the atom.
They orbit the nucleus in layers
called shells.

In an atom the number of positive protons is the same as the

number of negative electrons.
Nucleus contains protons and
neutrons, overall charge is
positive.
Most of an atoms mass is found
here.

Most of the atom is empty space.

Electrons give the atom it’s
overall size and shape.

An atom has no overall charge because the number of

positive protons is the same as the number of negative
electrons.
Click on this link to watch video about atom
Structure of the
Atom
Valence electrons
(participate in bonding) • Niels Bohr model of the atom
• Electrons –ve orbit nucleus in
discrete orbital shells
d p
s • Electrons have quantized positions, and
specific energies
• Stable configurations have full outer
shell

Nucleus contains Protons (1

Hyd rogen – 94 Plutonium)
and Neutrons.
Atomic mass ~ Protons +
Neutrons
The periodic
table Columns have similar valence structure

Adapted
from Fig. 2.6,
Callister 6e.

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
Bonding in
solids

• Primary bonding
• Ionic (ceramics – some covalent)
• Covalent (polymer C=C bonds)
• Metallic (metals)
• Secondary bonding (weaker)
• Van der Waals (polymers)
• Hydrogen (similar to VdW)

• We will consider the mechanisms and characteristics.

Ionic bonding –
origin •
Compounds of metallic and non-metallic elements
(e.g. NaCl, Al2O3, MgO, many ceramics)
• Requires electron transfer (+ve and –ve ions) and
large difference in electronegativity.
• Atomic number of Na = 11 (1 valence electron)
• Atomic number of Cl = 17 (7 valence electrons)

Na (metal) Cl (nonmetal)
Unstable unstable
electron

Nastable
(cation) - Cl
+ Coulombic (anion)
Attraction stable
Ionic bonding –
examples
NaCl
MgO
H He
2.1
Be CaF2 O F
-
Li 3.5 4.0 Ne
1.0 1.5 CsCl Cl -
Na Mg 3.0 Ar
0.9 Ti Cr Fe Ni Zn As Br -
1.2 1.8
K Ca 1.5 1.6 1.8 1.8 2.0 2.8 Kr
0.8 1.0 I -
Rb Sr 2.5 Xe
1.0 At -
Ba
0.8 2.2 Rn
Cs 0.9 -
0.7 Ra
Fr
Give
0.9 up electrons Acquire electrons
0.7
Ionic bonding –
characteristics
• Bonding is:
• Non-directional
• Relatively strong
• Material properties:
• Often ceramic (e.g. Alumina, Al2O3)
• High melting points (e.g. 2,200°C)
• High elastic modulus (e.g. E=400 GPa)
• Brittle (difficult for atoms to slide/ rearrange)
• Electrical and thermal insulators (no free
Covalent bonding –
origin
• Stable electron configurations by sharing electrons between
atoms
• Shared electrons belong to both atoms
• Typically non-metal compounds (polymers C-C & C-H bonds)

 E.g. Methane (CH4)

 C – has 4 valence e, needs 4
more
 H – has 1 valence e,
needs 1 more.
 Electronegatvities
are comparable
Covalent bonding –
examples
H2O

column IVA
H2 F2
C(diamond)
He
H
Cl2
2.1
Li Be
SiC C O F
-
Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.8 -
Rb Sr Sn As I Xe
0.8 1.0 1.6 1.8 1.8 2.5 -
2.0
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9 GaAs
Covalent bonding –
examples
• Compounds containing elements on
right side of table (GaAs, Si3N4)
• Non-metallic molecules (H2, Cl2)
• Some elemental solids (Si, C)
• C – Diamond
• Prevalent in polymers
• Occurs in ceramics
Covalent bonding –
characteristics
• Bonding is:
• Directional (exists in specific orientation)
• Very strong
• Material properties:
• Often polymers, glasses and ceramics (e.g. Diamond)
• Less dense than ionic/metallic bonded materials (directional
bonding makes is harder to
‘pack’ atoms)
• High elastic modulus (e.g. E~1000 GPa)
• High melting point (e.g. 3,550°C)
• Brittle (strong, directional atomic bonds)
• Electrical and thermal insulators
• …But polymers have low melting point and stiffness?...
Metallic bonding –
origins
• Metals and alloys
• Low number of valence electrons (1, 2, 3 from
each atom)
• Valence electrons become delocalized
• Electrons are not bound to any
particular atom

 Electrons are free to drift

throughout the metal
 ‘Sea of electrons’ around
positive ion cores
 High electrical conductivity
Metallic bonding-
characteristics
• Bonding is:
• Non-directional
• Intermediate strength
• Material properties:
• Metals (e.g. Aluminium – Al, Tungsten – W)
• Intermediate melting point (Al~660°C, W~3,410°C)
• Intermediate elastic modulus (Al~70, W~400 GPa)
• Close packing of atoms (high density)
• High electrical and thermal conductivity (free electrons)
• Ductile (planes of atoms can slide over each other).
Atomic bonding -
Summary
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Variable Directional
Covalent large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Variable
Metallic large-Tungsten Nondirectional (metals)
small-Mercury
Directional
Secondary smallest inter-chain (polymer)
inter-
molecular
Bonding in
materials
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E

Polymers Secondary bonding dominates

(Covalent & Secondary): small Tm
small E
 1.2 Crystal
Structure
Crystal Structure:
Atoms self-organize in crystals, most of the time.
The crystalline lattice, is a periodic array of the atoms.
Ex: metals, diamond and other precious stones, ice, graphite
e.t.c.

3D Structures 2D Structures
Few more 2D Structures:
Crystal Structure: (Amorphous)

When the solid is not crystalline, it is called amorphous. Ex:glass,

amorphous carbon (a-C), amorphous Si, most plastics
 Crystal Structure:
Crystal Structure: Unit Cell
The smallest structural unit of a crystal that has all its symmetry and by
repetition in three dimensions makes up its full lattice.
 Crystal Structure: Unit Cell
Source: https://pediaa.com
The Space Lattice and Unit
Cells
• Atoms, arranged in repetitive 3-Dimensional
pattern, in long range order (LRO) give rise to
crystal structure.
• Properties of solids depends upon crystal structure
and bonding force.
• An imaginary network of lines, with atoms at
Space Lattice
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. Unit Cell
amorphous materials
• Materials arranged in short
• According to Bravais (1811-1863) fourteen standard unit cells can describe all possible lattice
networks:

Pure metals are usually

body-centered cubic
(BCC), face-centered
cubic (FCC) or hexagonal
closed-packed (HCP)
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.

BCC Structure FCC Structure HCP Structure

Body Centered Cubic (BCC) Crystal
Structure
• Represented as one atom at each corner of cube and one at the center of cube.
• Each atom has 8 nearest neighbors.
• Therefore, coordination number is 8.
• Examples :-
 Chromium (a=0.289 nm)
 Iron (a=0.287 nm)

 Sodium (a=0.429 nm)

Figure 3.4 a&b

BCC Crystal Structure
(Cont..)
• 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
Therefore, lattice
constant a 4R
=
3
Atomic Packing Factor of BCC
Structure
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.
• Coordination number for FCC structure is 12
• Atomic Packing Factor is 0.74
• Examples :-
 Aluminum (a = 0.405)
 Gold (a = 0.408)

Figure 3.6 a&b

After F.M. Miller, “Chemistry: Structure and Dynamics,” McGraw-Hill, 1984, p.296
FCC Crystal Structure
(Cont..)
• Each unit cell has eight 1/8
atom at corners and six ½
atoms at the center of six
faces.
• Therefore each unit cell
has

(8 x 1/8)+
• Atoms contact(6 x ½)
each other
across cubic face diagonal
= 4R
Therefore, lattice
4constant
atoms a =
2
After F.M. Miller, “Chemistry: Structure and Dynamics,” McGraw-Hill, 1984, p.296
Hexagonal Close-Packed (HCP)
Structure
• 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.
• Atoms attain higher APF by attaining HCP structure than simple hexagonal
structure.
• The coordination number is 12, APF = 0.74.

Figure 3.8 a&b

After F.M. Miller, “Chemistry: Structure and Dynamics,” McGraw-Hill, 1984, p.296
HCP Crystal Structure
(Cont..)
• Each atom has six 1/6 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 ½) + 3 = 6 atoms
• Examples:-
 Zinc (a = 0.2665 nm, c/a = 1.85)
 Cobalt (a = 0.2507 nm, c.a = 1.62)

• Ideal c/a ratio is 1.633.

Figure 3.8 c
After F.M. Miller, “Chemistry: Structure and Dynamics,” McGraw-Hill, 1984, p.296
After F.M. Miller, “Chemistry: Structure and Dynamics,” McGraw-Hill, 1984, p.296
1.2 Solidification
● The crystallization of a large amount of material from a single
point of nucleation results in a single crystal.
● Single crystals are produced only under carefully controlled
conditions
● The expense of producing single crystal materials in only justified
for special applications – turbine engine blades, solar cells,
piezoelectric materials
● When a single material begins to solidify, multiple crystals begin
to grow in the liquid and a polycrystalline solid forms
1.2 Solidification
● The growth of crystal is known as nucleation, and the point
where it occurs is the nucleation point
● At the solidification temperature, atoms of a liquid, such as
melted metal, begin to bond together at the nucleation point and
start to form crystals
● The final sizes of the individual crystals depend on the number of
nucleation points
● The crystals increase in size by progressive addition of atoms and
grow until they impinge upon adjacent growing crystal.
1.2 Solidification
1.2 Solidification
● In engineering materials, a crystal is usually referred to as a grain
● A grain is merely a crystal without smooth faces because its
growth was impeded by contact with another grain or a
boundary surface.
● The interface formed between grain is called a grain boundary.
● The atoms between the grains (at the grains boundaries) have no
crystalline structure and are said to be disordered.
● Grains are sometimes large enough to be visible under an
ordinary light microscope or even to the unaided eye
● Rapid cooling generally results in more nucleation points and
smaller grains
● Slow cooling results in larger grains which have lower strength,
hardness and ductility.
1.3 Crystalline imperfections in solid
Why knowing solid imperfections is important?

● The properties of some materials are influenced by the presence

of imperfections
● Such an idealized solid does not exist, all contain large numbers
of various defects and imperfections
● Many of the properties of materials are sensitive to deviations
from crystalline perfection
● It is important to know types of imperfections and the roles they
play in affecting the behaviour of materials
1.3 Crystalline imperfections in solid
Crystalline defects
1.3 Crystalline imperfections in solid
Crystalline defects

● Referred to a lattice irregularity having one or more of its

dimensions on the order of an atomic order
● Classification is frequently made according to geometry of the
defect
● Examples of defects:
○ Point Defects
○ Impurities in solids
○ Dislocations – Linear Defects
1.3 Crystalline imperfections in solid
Point defects

● The simplest point defect is a

vacancy or vacant lattice site, from
which an atom is missing
● All crystalline solids contain
vacancies
● The existence of vacancies can be
explained by principle of
thermodynamics; in which the
presence of vacancies increases
the entropy of the crystals
1.3 Crystalline imperfections in solid
Point defects

● The equilibrium number of

vacancies:
1.3 Crystalline imperfections in solid
Impurities in solids
● It is impossible for a pure metal to consist only one type of atom
● Impurities or foreign atoms are always present, and some may exists as
crystalline defects
● Most familiar metals are not highly pure, rather they are alloys, in which
impurity atoms have been added intentionally to impart specific
characteristics to the materials
● Alloying is used in metals to improve
mechanical strength and corrosion resistance
1.3 Crystalline imperfections in solid
Dislocation-linear defects
● A dislocation is a linear or one-dimensional defect around which some of
the atoms are misaligned
● The magnitude and direction of the lattice distortion associated with a
dislocation are expressed in terms of a Burgers vector.
● Types:
○ Edge dislocation
○ Screw dislocation
○ Mixed dislocation
1.3 Crystalline imperfections in solid
Dislocation-linear defects
● Edge dislocation: a linear defect that centers on the
line that is defined along the end of the extra half-
plane of atoms. Sometimes is termed as dislocation
line.
● Within the region around the dislocation line there
is some localized lattice distortion.
● The atoms above the dislocation line are squeezed
together and those below are pulled apart
(reflected by the slight curvature for the vertical
planes of atoms as they bend around this extra-half
plane)
1.3 Crystalline imperfections in solid
Dislocation-linear defects
1.3 Crystalline imperfections in solid
Dislocation-linear defects

● Screw
dislocation:
Formed by a
shear stress
that is applied
to produce
the distortion
1.3 Crystalline imperfections in solid
Dislocation-linear defects

● The upper
front region of
the crystals is
shifted one
atomic
distance to
the right
relative to the
bottom
portion
1.3 Crystalline imperfections in solid
Dislocation-linear defects

● The atomic distortion

associated with a screw
dislocation is also linear
and along a dislocation
line, line AB
● Symbol to designate a
screw dislocation:
1.3 Crystalline imperfections in solid
Dislocation-linear defects

Mixed dislocation:

Most dislocation found in crystalline are neither pure edge nor pure
screw, but exhibit components of both types, terms as mixed
dislocation
1.4 Phase diagram
1.4 Phase diagram

Why knowing phase diagram is important?

● Engineer relates to the design and control of heat-treating
procedures
● Some properties of materials are functions of their
microstructures, and their thermal histories
● There is strong correlation between microstructure and
mechanical properties and the development of microstructure of
an alloy to the characteristics of its phase diagram
● Phase diagram provides valuable information about melting,
casting, crystallization and other phenomena
1.4 Phase diagram

Equilibrium and free energy

● Equilibrium is best described in terms of a thermodynamic

quantity called the free energy
● Free energy is a function of the internal energy of a system and
also the randomness or disorder of the atoms or molecules (or
entropy)
● A system is at equilibrium if its free energy is at minimum under
some specified combination of a temperature, pressure and
composition
● This means that characteristics of the system do not change with
time – system is table
1.4 Phase diagram
Phase equilibrium
● Equilibrium as it applied to system in which more than one phase
may exist.
● Phase equilibrium is reflected by a contact with time in the phase
characteristics of a system.

Types of phase diagram

● One component phase diagram
● Binary phase diagram
● Binary eutectic phase diagram
 1.4 Phase diagram
One component phase diagram
● Composition is held constant
● P-T phase diagram
1.4 Phase diagram
Binary phase diagram
● Binary alloys – two component
systems
● Represent the relationship
between temperature and
compositions and quantities of
phase equilibrium – influence
the microstructure of an alloy
● Phase transformation occur
when temperature is altered
 1.4 Phase diagram
Binary eutectic phase diagram
● Copper-silver system
● Has three single-phase
regions,
● – pure copper with silver
as solute solution
● – pure silver with copper
as solute solution
● Solubility of each phase is
limited. Below line BEG at
any temperature, only a
limited concentration of
silver dissolves in copper
and vice versa
1.4 Phase diagram
1.4 Phase diagram
1.4 Phase diagram