Introduction To Materials Science

and Engineering

MEng2091- Engineering Materials I

Prepared by Getachew G.
 Basic information
Course Title: - Engineering Materials I
Pre-requisites: No prerequisite

Course code: MEng2091

Academic year: 2019/20
Credit hours: 4(ECTS 5)
Target group: mechanical
Contact Hours: 2 lecture hrs.3tuterial hrs.
Semester I- year II
Course Instructor: Getachew G.
 The course enables students to understand:
 The main concept of engineering materials
 The influence of crystalline structure on the properties of
metal.
 Will acquire knowledge about type of defect and their
influences on the properties of crystals.
 How deformation will takes place and will know the main
types of plastic deformation

Course Objectives  The main causes for failure and types of failure. Methods to
overcome it.
 Will acquire knowledge about mechanical testing of
materials
 Main concepts of Phase and phase transformation,
crystalline changes and their influences on properties of
metals.
 Classification of engineering materials; Fundamental
theory of engineering materials: atomic structure,
Course bonds, crystalline structure; Defects in crystalline
Description structures and dislocation theory; Deformation in
solids; Failure and mechanisms of fracture; Mechanical
properties and testing of metals; Phases and phase
transformations.
 Chapter 1. Introduction
Historical perspective, Materials Science and Engineering, Classification of Materials

Chapter 2. Atomic structure and bonding

Fundamental concepts, bonding force and energies, primary inter atomic bonds and secondary

Chapter 3. Imperfections
bonding, molecules.

Imperfections in solids, point defects, impurities in solids, Miscellaneous imperfections (linear

Chapter 4. Dislocation and Strengthening Mechanisms
defects, interfacial defects, bulk or volume defects), Atomic vibrations, diffusion.

Course Contents
Chapter 5. Failure
Characteristics of Dislocations, Slip Systems, Slip in Single Crystals, Plastic Deformation of
Polycrystalline Materials, Mechanisms of Strengthening in Metal, Recovery, recrystallization
and Grain Growth.

Chapter 6. Mechanical Properties of Metals

Fundamentals of fracture, ductile fracture, brittle fracture, fracture mechanics, Impact Fracture
Testing , Cyclic Stresses, Crack Initiation and Propagation, creep

Chapter 7. Phase Diagrams

Concepts of Stress and Strain, Stress—Strain Behavior, Anelasticity, Elastic Properties of
Materials, Tensile Properties, Hardness, Design/Safety Factors

Solubility Limit, Phases, Microstructure, Equilibrium Phase Diagrams, Interpretation of phase

diagrams, The Iron–Iron Carbide (Fe–Fe3C) Phase Diagram, The Influence of Other Alloying
Elements, Phase Transformations in Metals
Pre-requisites No prerequisite

Semester 3rd

Status of Course Professional Compulsory

 Lectures supported by tutorials,

Teaching & Learning
 Assignments
Methods

Quizzes' 10%
Assignment 10%
Assessment & Mid exam 30%
Grading System Final exam 50%
 Minimum of 80% attendance during lecture hours, and 100%
Attendance
attendance during practical work sessions, except for some
Requirements
unprecedented mishaps.

References:
1. Materials Science and Engineering: An Introduction; W.D.
Callister, Jr. and D.G. Rethwisch, 9th edition, John Wiley and
Sons, Inc. (2013/14).
Literature 2. A. Flinn and Paul K. Trojan, Engineering Materials and their
applications, Dec 12, 1994
3. Michael Ashby, Hugh Shercliff, and David Cebon, Materials:

,
Engineering, Science, Processing and Design Mar 30, 2007

4. Yu Lakhtin, Engineering physical metallurgy & heat

treatment, 1990.
Engineering Material I
History of materials
Human Civilization is entirely depends on Materials.

Invention of Aero plane - 1902

 What are Materials?

Aluminum (metal) cans Glass (ceramic)

 A familiar item
that is fabricated
from three
different materials

Plastic (polymer) bottles

 Materials:- are substances from which something is made.
“The development of many technologies that make our
existence so comfortable has been intimately associated
with the accessibility of suitable materials.”

 Automobiles would not have  Sophisticated electronic

been possible without the devices rely on components
availability of inexpensive steel that are made from what are
or some other comparable called semiconducting
substitute. materials.
 What is Materials Science & Engineering?

 Material science is, the investigation of

the relationship among processing,
structure, properties, and performance of
materials.

 Material engineering is, on the basis of

structure & property correlations
designing or engineering the structure of
a material to produce a predetermined
set of properties.
  Because everything we use is made of materials; materials engineering
serves as the foundation for many engineering advances.
 Using science and engineering principles to select, design and
manufacture materials, materials engineers design, develop, fabricate
and evaluate materials for use in engineering applications.

 Materials engineers address the science and technology of producing

materials — including metals, ceramics, plastics, semiconductors and
composites — that have properties and shapes suitable for practical use
in applications including aerospace, transportation, electronics, energy
conversion, biomedical systems and sustainability.
 Classification

Materials

Metals/alloys Ceramics Composites Polymers

Iron
Titanium Nylon
Steel Alumina MMC
Polyester
Brass Silica GFRC
Polyethylene
Aluminum Glass CFRC
Bakelite
Synthetic materials:- Non – metallic materials that do not exist in

nature, although they are manufactured from

natural substances.

Natural materials:- Exist in nature such as oil, coal clay and wood.
 Introduction Cont’d…
• The ability of materials to undergo forming by different
techniques is dependent on their structure and
properties.
• Behavior of materials depends on their structure-atomic
structure, crystal structure and grain structure.
• Materials are generally classified into metals/alloys and
non-metals such as plastics, ceramics, composites.
• Metals are further classified into ferrous and nonferrous
metals.
• Further, materials can be classified into crystalline and
amorphous materials.
 understanding the structure-composition-properties lead to
a remarkable progress in properties of materials.
 E.g. the strength/density ratio of materials, resulted in a
variety of new products, from dental materials to tennis
racquets.
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Structure:- The arrangement of the internal components of a material.

 To change the performance of materials, modification of

the internal structure is required
Structure, Processing, & Properties
• Properties depend on structure
ex: hardness vs structure of steel

• Processing can change structure

ex: structure vs cooling rate of steel
Types Of Materials
Metals:
– Strong, ductile
– High thermal & electrical conductivity
– Opaque, reflective.

Polymers/plastics:
- Covalent bonding  sharing of e’s
– Soft, ductile, low strength, low density
– Thermal & electrical insulators
– Optically translucent or transparent.

Ceramics:
– ionic bonding (refractory) – compounds of metallic &

non-metallic elements (oxides, carbides, nitrides, sulfides)

– Brittle, glassy, elastic, Non-conducting (insulators).
ADVANCED MATERIALS
 Materials that are utilized in high-technology application
 High-tech, a device or product that operates or functions using
relatively intricate and sophisticated principles
 Electronic equipment, computers, fiber optic systems,
spacecraft, aircraft, and military rocket.
 They might be of all material types whose properties have
been enhanced or newly developed.
E.g.  Semiconductors: electronics and computer industries.

 Biomaterials: bio-compatibility with body tissues.

 Smart Materials: able to sense the environment (force, pressure)

e.g. sensor and actuator.
 Nanomaterials: fascinating property due to their size e.g. Nano
carbons, Fullerenes, carbon nanotubes, etc.
 Modern Materials Needs
 The development of more sophisticated and specialized materials,
as well as consideration of the environmental impact of material
production.

 Nuclear energy: many problem remain in materials, from fuel to

containment structures to facilities to the disposal of radioactive
waste.
 Transportation: facing low operating temperature engine etc.
 Fuel cell energy: facing low operating temperature for high
energy output.
 Manufacturing process: facing toxic as a product of the process

 Non renewable materials such as polymer, some of metals, oil will

be depleted for:

 The discovery of additional reserves,

 The development of new materials having comparable
properties with less adverse environmental impact, and/or
 Increased recycling effort and the development of new
recycling technology
 Why we Study Material Engineering?
• Engineer at one time or another exposed to a design
problem involving materials

• E.g. design of transmission gear, the superstructure for a

building, an integrated circuit chip.

• Every product is made of materials and energy is involved

in the production and in use.

• Many times, a materials problem is one of selecting the

right material from the thousands available. E.g. Availability,
service condition and cost.

• This is why all Engineers have to study materials science

during their undergraduate study
 Crystalline Structure
• Crystalline materials have atoms arranged symmetrically in long
range order.
• In amorphous materials there is short range order, the orderly
arrangement of atoms being discontinuous.
• Crystalline solids have their atoms arranged in three dimensional
space in basic forms called lattices – Bravais lattices.

Fig. 1 a) Crystalline structure b) Amorphous structure

 Cont’d…
• There are basically 7 lattice/crystal systems, namely, Cubic, hexagonal,
tetragonal, orthorhombic, rhombohedral, monoclinic, triclinic.
• Crystal structures of commonly used engineering metals and alloys can
be grouped into three types, namely, body centered cubic [BCC], face
centered cubic [FCC] and hexagonal closed pack [HCP].
• The smallest group of stacked atoms which repeats itself in three
dimensional space and hence fixes the lattice structure can be defined
as unit cell.Table 1 The Seven Different Crystal Lattice Systems
 Cont’d…
• Physical and mechanical characteristics of crystalline
solids are dependent on the effective number of atoms
in a unit cell, density and orientation of packing of
atoms within the unit cell.
• Unit cells are represented by hard-ball models.
• The effective number of atoms in a unit cell represents
the extent of packing of atoms and void space within the
unit cell.
 Cont’d…

Ex. Aluminum, Copper,

Lead, Nickel, Iron, Gold,
Silver
Packing efficiency = 74%
Basic atoms = 4

Ex. Chromium,
Molybdenum, Niobium, Ex. Beryllium, Cadmium,
Tungsten, Iron. Magnesium, Zinc.
Packing efficiency = 68% Packing efficiency = 74%
Basic atoms = 2 Basic atoms = 6

Fig. 2 Unit cell structures of Cubic and HCP lattices

 Crystalline structure Cont’d…

Where a=
lattice
constant
R= atomic
radius
D= atomic
dia
Figure 3. Body centered cubic unit cell. Relation between a and D.

Figure 5. Hexagonal
structure with unit cell
outlined, and showing
relationship between a and
c.
Figure 4. Face centered cubic unit cell. Relation between a and D.
Why Study The Structure of Crystalline Solids?
 Because, the properties of some materials are directly related to
their crystal structures.

 Significant property differences exist between crystalline and

noncrystalline materials having the same composition, diamond
Vs graphite

Crystalline and Crystal Structure

 A crystalline material is one in which the atoms are situated in a specific

order (repeating or periodic array over large atomic distances).

 Leads to structure displaying

 Long-range Order that is Measurable and Quantifiable

 Some of the properties of crystalline solids depend on the crystal structure

(manner in which atoms, ions or molecules are spatially arranged) of the material
 It is long range order

It is short range order

All metals, many ceramics, and some polymers make crystalline structure

 Ice, NaCl are crystalline solids; the glass for drinking water is an
amorphous solid. Heat-treatment makes glass partly crystalline so
that it becomes transparent. Nylon, polypropylene are crystalline
polymers.
 When describing crystalline structures, atoms are considered as
being solid spheres having well-defined diameters
 Atomic hard sphere model => in which spheres representing nearest-
neighbor atoms touch one another.
Unit Cell
• Is the smallest group of atoms whose repetition
makes a crystalline solid.
• Is the basic structural unit or building block of the
crystal structure
• Is chosen to represent the symmetry of the crystal
structure
Types of Solids
 Depend on the arrangement of atoms or ions with respect to one another.

1. Crystalline material: periodic array

2. Single crystal: periodic array over the entire extent of the material
3. Polycrystalline material: many small crystals or grains

4. Amorphous: lacks a systematic (periodic) atomic arrangement

 Lattice is a regularly spaced 3D array

of points coinciding with atom

positions (or centers).
Metallic Crystal Structures
Three common metallic crystal structure
1. The Face-Centered Cubic Crystal Structure
2. The Body-Centered Cubic Crystal Structure
3. The Hexagonal Close-Packed Crystal Structure

Face-Centered Cubic Structure (FCC)

 FCC => a unit cell of cubic geometry, with atoms located at each of the
corners and the centers of all the cube faces.
 For the fcc crystal structure, each corner atom is shared among eight
unit cells, whereas a face-centered atom belongs to only two atom.
 Atoms located at corners and on centers of faces
 Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.
How many atoms in a unit cell of FCC?
 one-eighth of each of the eight corner atoms and one-half of each of
the six face atoms, or a total of four whole atoms, may be assigned to
a given unit cell.
 E.g. gamma iron, aluminum, copper, nickel, lead, silver, gold and
platinum have fcc
 Cell volume= cube volume (generated from the center of atom at corner)

hard sphere model for The face- centred cubic (fcc) crystal structure: (a) hard-ball
the FCC unit cell model; (b) unit cell; and (c) single crystal with many unit cells
 The number of atoms per unit cell, N, can be computed using them
following formula:

where
Ni , the number of interior atoms
Nf , the number of face atoms
Nc , the number of corner atoms

For the FCC crystal structure, there are eight corner atoms (Nc = 8),
six face atoms (Nf = 6), and no interior atoms (Ni = 0). Thus,

or a total of four whole atoms may be assigned to a given unit cell.

 FCC can be represented by a stack of close-packed planes (planes with

highest density of atoms)
Two other important characteristics of a crystal structure are the
coordination number and the atomic packing factor (APF).

 For metals, each atom has the same number of touching atoms,

which is the coordination number,

 For fcc, coordination number is 12.

 Atomic Packing Factor (APF) is the sum of the sphere volumes of

all atoms within a unit cell divided by the unit cell volume

 For the FCC structure, the atomic packing factor is 0.74, which is the
maximum packing possible for spheres all having the same diameter.

The coordination number of a central atom in a molecule or crystal is the

number of its nearest neighbors
Derive

Where a = side length of the unit cell cube

R = Radius of the atom sphere
From right angle triangle:

Solving for a:

The FCC unit cell volume:

 APF for FCC

Considering atom as a sphere:

atoms volume
4
unit cell 4 p R3 atom
3
APF =
3 volume
a
unit cell

Volume of cell:

Finally,
 Body-Centered Cubic Structure (BCC)
 A cubic unit cell with atoms located at all eight corners and
a single atom at the cube center.
 Center and corner atoms touch one another along cube
diagonals.
 All atoms are identical; the center atom is shaded differently
only for ease of viewing.

bcc crystal structure: (a) hard-ball model; (b) unit cell;

and (c) single crystal with many unit cells
E.g. of BCC structure - alpha iron, chromium, molybdenum, tantalum, tungsten, and vanadium.
 For BCC unit cell, derive that the side length a obeys the relation:

Where a = side length of the unit cell cube

R = Radius of the atom sphere

 No of atoms in BCC unit cell

 The coordination number = number of closest neighbors = number

of touching atoms = 8.
 The atomic packing factor for BCC is lower than FCC — 0.68 versus
0.74, because BCC has less coordination number.
Prove that APF for BCC unit cell is 0.68

Close-packed directions:
length = 4R = 3 a

= 0.68
Hexagonal Close-Packed Crystal (HCP)

 Each of top and bottom faces of the unit cell consist of 6 atoms
that form regular hexagons and surround a single atom in the
center
 Another plane that provides 3 additional atoms to the unit cell is
situated between the top and bottom planes
 The atoms in this mid-plane have as nearest neighbors atoms
in both of the adjacent two planes
  The equivalent of six atoms is contained in each unit cell.
 If a and c represent, respectively, the short and long unit cell
dimensions the c/a ratio should be 1.633.
 The coordination number and the APF for the HCP are the same
as for FCC: 12 and 0.74, respectively

 The number of atoms per unit cell for the HCP crystal structure

 Thus, 6 atoms are assigned to each unit cell.

E.g.- beryllium, cadmium, cobalt, magnesium, alpha titanium, zinc

and zirconium.
Simple cubic (SC) crystal structure

 Atoms situated only at the corners of a cube.

 Rare due to low packing density (only polonium element has

this structure.

 The coordination number is 6, which is the nearest neighbors

 No of atom/unit cell = 8 corners x 1/8 = 1

For the simple cubic

crystal structure,
(a) a hard-sphere
unit cell, and
(b) a reduced-
sphere unit cell.
SCC BCC

FCC HCP
Close-packed Crystal Structures

 FCC and HCP may be generated by the stacking of close-packed

planes. The difference is in the stacking sequence
 These two crystal structures may be described in terms of close-
packed planes of atoms (i.e., planes having a maximum atom or
sphere- packing density).
HCP: Stacking Sequence ABABAB... FCC: Stacking Sequence ABCABCABC...

Third plane placed above “holes” of first

Third plane placed directly above first plane of atoms plane not covered by second plane
 Ex1.

1. The atomic radius of an iron atom is 1.238 * 10-10 m.

Iron crystallizes as BCC. Calculate the lattice parameter
of the unit cell, a. How many atoms are contained within
the BCC unit cell ? Also find the atomic packing
efficiency ?
2. Show that A.P.E of FCC & HCP structured materials is
74%.
Reasons for dense packing in metallic crystal structure

- 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.

- Electron cloud shields cores from each other

 Density Computations
 Density of a material can be computed from its crystalline structure
Where
n = number of atoms associated with each unit cell
A = atomic weight
VC = volume of the unit cell

NA = Avogadro’s number (6.023 × 1023 atoms/mol)

Theoretical Density Computation for Copper
Copper has an atomic radius of 0.128 nm, an FCC crystal structure, and an atomic
weight of 63.5g/mol. Compute its theoretical density and compare the answer with its
measured density.
Solution:
The crystal structure is FCC, n (atoms) = 4; ACu = 63.5g/mol, VC = a3 = [ 2R(2)1/2]3 (For
FCC)= 16R3(2)1/2 ; R (atomic radius) = 0.128nm.
Using the equation:
=
,The literature value = 8.94g/cm3
Crystal Systems
 Unit cell: smallest repetitive volume which contains the complete
lattice pattern of a crystal.
 The unit cell geometry is completely defined in terms of six
parameters: the three edge lengths a, b, and c, and the three
interaxial angles α, β and, γ. This is termed as lattice parameters
or lattice constants.

A unit cell with x, y, and z coordinate

axes, showing axial lengths (a, b, and c)

and interaxial angles (α, β and, γ).

The seven crystal systems
Based on their length equality or inequality (a, b, and c ) and their
orientation ( the angles between them α, β and, γ ) a total of 7 crystal
systems can be defined.
cubic Tetragonal Orthorhombic

Monoclinic Rhombohedral Hexagonal

Triclinic
Bravais Lattices

 Many of the seven crystal systems have variations of the basic

unit cell.

 August Bravais (1811-1863) showed that 14 standards unit cells

could describe all possible lattice networks.

 From 7 crystal systems, with the centering (face, base and body

centering), 14 kinds of crystal lattices, known as Bravais lattices,

can be generated.

 In geometry and crystallography, a Bravais lattice is an infinite set

of points generated by a set of discrete translation operations.

Crystal system Bravais Lattices

cubic

Tetragonal

Orthorhombic
Crystal system Bravais Lattices

Monoclinic

Rhombohedral

Hexagonal

Triclinic
 Crystal: is a 3D translationally periodic arrangement of atoms
 Lattice: is a 3D translationally periodic arrangement of points
 Basis or Motif: is atom or group of atoms associated with each lattice
points

Crystal = Lattice + Motif

Lattice Crystal

+ Motif =


 Lattice: how to repeat

 Motif: what to repeat
Crystallographic Points, Directions, and Planes
POINT COORDINATES

 Position of any point in a unit cell is given by its coordinates or distances

from the x, y and z axes in terms of the lattice vectors a, b and c and
point coordinate indices: q, r, and s.

 qa = lattice position referenced to the x axis

 rb = lattice position referenced to the y axis
 sc = lattice position referenced to the z axis

The manner in which the q, r, and s coordinates

at point P within the unit cell are determined. The
q coordinate (which is a fraction) corresponds to
the distance qa along the x axis, where a is the
unit cell edge length. The respective r and s
coordinates for the y and z axes are determined
similarly.
EXAMPLE PROBLEM
 Specify coordinate indices for all numbered points of the unit cell in the
illustration.
Crystallographic Directions

 A crystallographic direction is defined as a line directed between

two points, or a vector.
 The directions in a crystal are given by specifying the coordinates
(u, v, w) of a point on a vector (ruvw) passing through the origin.

ruvw = ua + vb + wc, It is indicated as [uvw].

 For example, the direction [110] lies on a vector r110 whose projection
lengths on x and y axes are one unit (in terms of unit vectors a and
b).
 Directions of a form or family like [110], [101], [011] are written as
angle brackets <110>.
To determine a direction of a line in the crystal
1. Find the coordinates of the two ends of the line and subtract the
coordinates (Head – Tail) OR draw a line from the origin parallel to
the line and find its projection lengths on x, y and z axis in terms of
the unit vectors a, b and c.
2. Convert fractions, if any, in to integers and reduce to lowest term.
3. Enclose in square brackets [uvw], No commas.

The [100], [110], and [111] directions within a unit cell.

 The line which passes through uvw will also pass through 2u 2v 2w
and ½ u ½ v ½ w. Hence [uvw], [2u 2v 2w] and [½ u ½ v ½ w] are
same and written as [uvw].
 Fractions are converted in to integers (as shown in the figure below)
and reduced to lowest terms.
EXAMPLE PROBLEM
Determine the indices for the direction

Within the following unit cell draw a [110] direction with its tail located at the origin of
the coordinate system, point O.
Directions in Hexagonal Crystal
 directions in the hexagonal system are also written in terms of
four indices as [uvtw].

 Ruled-net coordinate axis system for hexagonal unit cells that may
be used to plot crystallographic directions.
 If [UVW] are indices in three EXAMPLE PROBLEM
axes then it can be converted to
four- axis indices [uvtw] using
the following relations.

U=u–t
V=v–t
u = (2U-V)/3
v = (2V-U)/3
t = -(u + v) = -(U +
V)/3
W=w
Crystallographic Planes
To find the Miller Indices of a plane, follow these steps:

1. Determine the intercepts of the plane along the crystal axes

2. Take the reciprocals

3. Clear fractions

4. Reduce to lowest terms and enclose in brackets ()

Ex: Intercepts on a, b, c : ¾, ½, ¼ (h k l) = (4/3, 2, 4) = (2 3 6)

Planes can also have negative intercept e.g. 1, -1/2, 1, h k l = 1 -2 1.

This is denoted as
Representations of a series
each of the (a) (001), (b) (110),
and (c) (111) crystallographic
planes.
Example: Miller indices for plane A
1. Find the intercepts x = 1, y = 1, z = 1
2. Find the inverse 1/x=1, 1/y=1, 1/z=1
3. No fractions to clear
4. (1 1 1)
Exercise

Notes About the Use of Miller Indices for Planes

 A plane and its negative are parallel and identical.
 Planes and its multiple are parallel planes:
 (100) is parallel to the plane (200) and the distance between
(200) planes is half of the distance between (100) planes.
Family of planes {hkl}

 Planes having similar indices are equivalent, means having the

same atomic packing e.g. faces of the cube (100), (010) and (001).
 This is termed as a family of planes enclosed in braces and denoted
as {100} which includes all the (100) combinations including negative
indices.

Note the shift of origin

from blue to red circle
for the negative indices.

Horizontally equivalent
Planes in Hexagonal system

 In the cubic system all the faces of the cube are equivalent, that is, they
have similar indices.
 However, this is not the case in the hexagonal system. The six prism
faces for example have indices (1 0 0), (0 1 0),

 In order to address this, a fourth axis (a3) which is opposite to the vector
sum of a1 and a2 is used and a corresponding fourth index i is used
along with hkl. Therefore the indices of a plane is given by (hkil) where

i = -(h+k).
 Sometime i is replaced with a dot and written as (h k . l)
Interplanar spacing
Polymorphism and Allotropy

 Polymorphism: Some materials can exist in more than one

crystal structure.
 E.g., Iron has BCC structure at room temperature , but FCC
structure at 912C.
 Allotropy: a property exhibited by some elements of existing
in multiple forms with different atomic structures under P &T.
 E.g., C has two allotropes: Graphite is formed at room
temperature and Diamond is formed at high temperature and
pressure.
 Note the difference in properties due to change in crystal
structure of same metal/element.
 Most often a modification of the density and other physical

properties accompanies a polymorphic transformation.

Single Crystals
 For a crystalline solid, when the repeated arrangement of atoms is
perfect or extends throughout the entirety of the specimen without
Interruption, the result is a single crystal
 If the extremities of a single crystal are permitted to grow without
any external constraint, the crystal will assume a regular geometric

shape having flat faces

 Within the past few years, single crystals have become extremely
important in many of our modern technologies
 Single crystals exist in nature, but they may
also be produced artificially.
 They are ordinarily difficult to grow, because
the environment must be carefully controlled
Garnet
Polycrystalline Materials
 Most crystalline solids are composed of a collection of many
small crystals or grains; such materials are termed polycrystalline
 Initially, small crystals or nuclei form at various positions. many
small crystals (grains) with varying orientations.
 Atomic mismatch where grains meet (grain boundaries).
 Upon completion of solidification, grains having irregular shapes
have formed.
Anisotropy
 The property of materials being directionally dependant.
 Different directions in a crystal have different packing. Causes anisotropy
in crystal properties E.g. deformation, in direction of applied force.
 The physical properties of single crystals of some substances depend on
the crystallographic direction.
 The extent and magnitude of anisotropic effects in crystalline materials
are functions of the symmetry of the crystal structure
 For example, the elastic modulus, the electrical conductivity, and the index
of refraction may have different values in the [100] and [111] directions.
Modulus of Elasticity Values for Several Metals at Various Crystallographic Orientations
  Anisotropy is associated with the variance of atomic or ionic spacing with
crystallographic direction.
 The degree of anisotropy increases with decreasing structural symmetry—
triclinic structures (having three unequal crystal axes) normally are highly anisotropic.
 The magnetic properties of some iron alloys used in transformer cores are
anisotropic.
 Some polycrystalline materials have grains with preferred orientations (texture)

are exhibits anisotropic properties

Isotropy
 Substances in which measured properties are independent of the direction of
measurement.
 The property of material being identical or having the same physical property,
in all directions.
 If grain orientations are random  bulk properties are isotropic.
Noncrystalline (Amorphous) Solids

 Non-crystalline solids lack systematic and regular arrangement of

atoms over relatively large atomic distances. Also called amorphous
(without form).
 No long-range order, Nearly random orientations of atoms.

Comparison of SiO2
 Crystalline structure has ordered atoms while non-crystalline structure
has disorder atoms.
 Each Si atom is bonded to 3 - O atoms in crystalline as well as non-
crystalline structures.

Two-dimensional schemes of the structure of (a) crystalline silicon dioxide and (b) noncrystalline
 X-ray Diffraction: Determination Of Crystal Structures
 X-rays are a form of electromagnetic radiation that have high energies and short
wavelengths—wavelengths on the order of the atomic spacings for solids.
 When a beam of x-rays impinges on a solid material, as shown below, a portion of
this beam is scattered in all directions by the electrons associated with each atom
or ion that lies within the beam’s path (P &Q).
 The scattered rays 1’ and 2’ occurs also at an angle θ to the planes if the path length
difference between 1–P–1’ and 2–Q–2’ (i.e., SQ + QT) is equal to a whole number, n,
of wavelengths— that is, the condition for diffraction is nλ = SQ + QT

Is known as Bragg’s law

a is edge length

Interplanar spacing for a plane having

Diffraction of x-rays by planes of atoms (A–A and B–B). indices h, k, and l
Table: X-Ray Diffraction Reflection Rules and Reflection Indices, for Body Centered,
Cubic, Face-Centered Cubic, and Simple, Cubic Crystal Structures

This figure shows a diffraction pattern for a powdered specimen of lead.

The high-intensity peaks result when the Bragg diffraction condition is satisfied by
some set of crystallographic planes. These peaks are plane-indexed in the figure.
Example
Uses of x-ray diffractometry
 determination of crystal structure.

 The unit cell size and geometry

 crystallographic orientations of single crystals

 qualitative and quantitative chemical identifications

 determination of residual stresses and crystal size.

See the figure below.
END
WHY Study Imperfections in Solids?
 The properties of some materials are influenced by the presence
of imperfections.

 For example, the mechanical properties of pure metals experience

significant alterations when the metals are alloyed (i.e., when impurity
atoms are added)—for example, brass (70% copper & 30% zinc) is much
harder and stronger than pure copper.

 Integrated-circuit microelectronic devices found in our computers,

calculators, and home appliances function because of highly controlled
concentrations of specific impurities that are incorporated into small,
localized regions of semiconducting materials.

 Crystal imperfections have strong influence upon many properties of

crystals, such as strength, electrical conductivity and hysteresis loss
of ferromagnets.
 Imperfections or defects
 Any deviation from the perfect atomic arrangement in a crystal.
 Real crystals are never perfect:- there are always defects.
 Defects have a profound impact on the macroscopic properties of materials.
 defects do not necessarily have adverse effects on the properties of materials.
 Controlling the defects is one of the main goal of materials science and
engineering!
 Many of the important properties of materials are due to the presence
of imperfections.

A crystalline defect refers to a lattice irregularity having one or more

of its dimensions on the order of an atomic diameter.
Types of Defects
 Defects may be classified into four categories depending on their

dimension:

0D, Point defects: atoms missing or in irregular places in the lattice

(vacancies, interstitials, impurities)

1D, Linear defects: groups of atoms in irregular positions (e.g. screw

and edge dislocations)

2D, Planar defects: the interfaces between homogeneous regions

of the material (grain boundaries, external surfaces)

3D, Volume defects: extended defects (pores, cracks)

Types of Defects
Point Defects
 The simplest of the point defect is a vacancy, or vacant lattice site.

 All crystalline solids contain vacancies.

 Principles of thermodynamics is used explain the necessity of the existence

of vacancies in crystalline solids.

 The presence of vacancies increases the entropy (randomness) of the crystal.

Vacancies & self-interstitials defect

 Vacancy - a lattice position that is vacant (empty
spaces) because the atom is missing. vacancies
arise from thermodynamics (entropy)
 Interstitial - an atom that occupies a place outside
the normal lattice position. It may be the same
type of atom as the others (self-interstitial) or an
Two-dimensional representations
impurity interstitial atom. of a vacancy and a self-interstitial
 A substitutional impurity atom is an atom of a different type than the bulk
atoms, which has replaced one of the bulk atoms in the lattice. Substitutional
impurity atoms are usually close in size (within approximately 15%) to the bulk
atom.
 An example of substitutional impurity atoms is the zinc atoms in brass. In
brass, zinc atoms with a radius of 0.133 nm have replaced some of the
copper atoms, which have a radius of 0.128 nm.
 Interstitial impurity atoms are much smaller than the atoms in the bulk matrix.
Interstitial impurity atoms fit into the open space between the bulk atoms of the
lattice structure.
Metallic materials have
relatively high atomic Two-dimensional
packing factors, which schematic
means that interstitial representations
positions are relatively of substitutional
small and have smaller and interstitial
impurity atoms.
atomic diameter.
Schottky and Frenkel Defect
The combination of anion cation vacancies (in pairs) is called Schottkey imperfections.
The combination of a vacancy and interstitial is called a Frankel imperfection.

 Frenkel Defect
-- a cation vacancy-cation interstitial pair

 Schottky Defect Happened when an

-- a paired set of cation and anion vacancies atom being free from
regular site, migrates
Schottky
Defect: through successive
steps and eventually
settles at the crystal

Frenkel surface and finally it

Defect is electrically neutral.

 Equilibrium concentration of defects  e  QD /kT

A self-interstitial is an atom from the crystal that is crowded into an interstitial site—a
small void space that under ordinary circumstances is not occupied. In metals, a self-
interstitial introduces relatively large distortions in the surrounding lattice because the atom
is substantially larger than the interstitial position in which it is situated. Consequently, the
formation of this defect is not highly probable, and it exists in very small concentrations that
are significantly lower than for vacancies .

 The equilibrium number of vacancies formed as a result of thermal vibrations may be

calculated from thermodynamics:(an Arrhenius model)

 The number of vacancies increases exponentially with temperature—that is, as T

.
increases, so also does the term exp(-Qv/kT).
 For most metals, the fraction of vacancies Nv/N just below the melting temperature
is on the order of 10^-4—that is, one lattice site out of 10,000 will be empty.
 Example Problem
Calculate the equilibrium number of vacancies per cubic meter for copper at 1000°C.
The energy for vacancy formation is 0.9 eV/atom; the atomic weight and density (at
1000 ° C) for copper are 63.5 g/mol and 8.4 g/cm3, respectively.
Solution
given
T = 1000°C , Qv = 0.9 eV/atom, Acu = 63.5 g/mol, ρ = 8.4 g/cm3 , K
=1.38 × 10^-23 J/atom-K = 8.62 × 10^-5 eV/atom-K, NA = 6.023 × 1023 atoms/mol,
The number of regular lattice sites
N A  (6.023x10 23 atoms / mol )(8.4 g / cm 3 )(106 cm 3 / m 3 )
N  
ACu 63.5 g / mol
 8.0x1028 atoms / m 3
Thus, the number of vacancies at 1000 C (1273K ) ie equal to

The equilibrium number of vacancies

 Q 
N v  N exp  v 
 kT 
 (0.9eV 
 (8.0x10 28 atoms / m 3 ) exp
 (8.62 x10 5 eV / K )(1273 K ) 

 
 2.2x10 25 vacancies/m 3

And Note: for MOST MATERIALS just below Tm  Nv/N = 10-4

Here: 0.0022/8 = .000275 = 2.75*10-4
Substitutional Solid Solutions

For fcc, bcc, hcp structures

the voids (or interstices)
between the host atoms are
relatively small ⇒ atomic
radius of solute should be
significantly less than solvent
Interstitial Solid Solutions
Interstitial solid solution of C in
α-Fe. The C atom is small
enough to fit, after introducing
some strain into the BCC
lattice.
IMPURITIES IN SOLIDS
Impurities - atoms which are different from the host
 All real solids are impure. Very pure metals 99.9999%- one impurity per
10^6 atoms
 May be intentional or unintentional
 Examples: carbon added in small amounts to iron makes steel, which is
stronger than pure iron. Boron added to silicon change its electrical properties.
Alloys - deliberate mixtures of metals
 Example: The commercial (sterling) silver is 92.5% silver – 7.5% copper.
 Silver alloy is stronger than pure silver.
 Impurity atoms have been added intentionally to impart specific characteristics
to the material.
 In normal ambient environments, pure silver is highly corrosion resistant, but
also very soft. Alloying with copper significantly enhances the mechanical
strength without depreciating the corrosion resistance appreciably.
Solid Solutions
Solid solutions forms when, the solute atoms are added to the host material,
the crystal structure is maintained and no new structures are formed.
 Compositionally homogeneous; the impurity atoms are randomly and
uniformly dispersed within the solid.
 Substitutional and interstitial Impurity point defects are found in solid
solutions
 The ability to dissolve is called solubility.

Solvent is the element or compound that is present in the greatest amount; on

occasion, solvent atoms are also called host atoms.

Solute is used to denote an element or compound present in a minor

concentration.
Factors for high solubility Hume – Rothery rules
1. Atomic size factor. atoms need to “fit” ⇒ solute and solvent atomic radii should
be within ~ 15%. Otherwise, the solute atoms create substantial lattice
distortions and a new phase forms.
2. crystal structure. For appreciable solid solubility, solute and solvent should be
the same
3. Electronegativity factor. Electronegativities of solute and solvent should be
comparable (otherwise new inter-metallic phases are encouraged).
4. Valences. Other factors being equal, a metal has more of a tendency to dissolve
another metal of higher valency than to dissolve one of a lower valency.

For example copper and nickel, elements are completely soluble in one another at all
proportions, the atomic radii for copper and nickel are 0.128 and 0.125 nm, respectively;
both have the FCC crystal structure; and their electronegativities are 1.9 and 1.8. and
valences are +1 for copper (although it sometimes can be +2) and +2 for nickel.
For interstitial solid solutions, impurity atoms fill the voids or interstices among the
host atoms. For both FCC and BCC crystal structures, there are two types of
interstitial sites—tetrahedral and octahedral—these are distinguished by the
number of nearest neighbor host atoms—that is, the coordination number.
Tetrahedral sites have a coordination number of 4; straight lines drawn from the
centers of the surrounding host atoms form a four-sided tetrahedron.

Figure 4.3 Locations of tetrahedral and octahedral interstitial sites within (a) FCC and (b) BCC unit
cells.
However, for octahedral sites the coordination number is 6; an octahedron is produced by joining
these six sphere centers. For FCC, there are two types of octahedral sites with representative point
coordinates of 0 ½ 1 and 1/2 ½ 1/2. Representative coordinates for a single tetrahedral site type are
¼ ¾ ¼. Locations of these sites within the FCC unit cell are noted in Figure 4.3a. One type of each
of octahedral and tetrahedral interstitial sites is found for BCC. Representative coordinates are as
follows: octahedral, ½ 1 0 and tetrahedral, 1 1/21/4. Figure 4.3b shows the positions of these sites
within a BCC unit cell.
 Specification Of Composition
The composition / concentration/ of an alloy is expressed in terms of:
 weight percent (wt%) is the weight of a particular element relative to the
total alloy weight. For two-component system, concentration of element 1 in wt. %
is
wt m1 where m1 and m2 represent the
C1  x 100 weight (or mass) of elements 1
m1  m2
and 2, respectively

 Atom percent (At%) is the number of moles of an element in relation to the

total moles of the elements in the alloy. For two-component system, concentration
of component 1 in at. % is

at nm1 where nm1 = m’1/A1, m’1 is mass

C1 x 100 in grams of component 1, A1 is
nm1  nm 2
atomic mass of component 1
Wt. % and At. % -- An example
Typically we work with a basis weight (100g or 1 kg) or moles
given: alloy by weight -- 60% Cu, 40% Ni
600 g
nCu   9.44m
63.55 g / m
Atom percent
400 g
nNi   6.82m computations also can be
58.69 g / m
carried out on the basis of
9.44
CCu 
'
 .581 or 58.1% the number of atoms
9.44  6.82
6.82 instead of moles, because
CNi 
'
 .419 or 41.9%
9.44  6.82 one mole of all substances
contains the same number
of atoms.
Dislocations—linear Defects
 A dislocation is a linear or one-dimensional defect around which some
of the atoms are misaligned.
 The interatomic bonds are significantly distorted only in the immediate
vicinity of the dislocation line. This area is called the dislocation core.
 Dislocations also create small elastic deformations of the lattice at large
distances.
 Dislocations are very important in mechanical properties of Material

Atomic view of
edge dislocation
motion from left to
right as a crystal
is sheared.

Figure 4.4 The atom positions around an edge dislocation; extra half-plane of atoms shown in perspective.
Linear Defects (Dislocations)
– Are one-dimensional defects around which atoms are
misaligned

• Edge dislocation:
– extra half-plane of atoms inserted in a crystal structure
– b perpendicular () to dislocation line

• Screw dislocation:
– spiral planar ramp resulting from shear deformation
– b parallel () to dislocation line
• Burger’s vector, b: measure of lattice distortion
Burgers Vector
 To describe the size and the direction of the main lattice distortion
caused by a dislocation we should introduce so called Burgers vector b.

 To find the Burgers vector, we should make a circuit from atom to

atom counting the same number of atomic distances in all directions.
If the circuit encloses a dislocation it will not close. The vector that
closes the loop is the burgers vector b.

 For metallic materials, the Burgers vector for a dislocation points in a close-
packed crystallographic direction and is of magnitude equal to the interatomic
spacing.
The atomic distortion associated with a screw dislocation is also linear and
along a dislocation line, line AB in Figure 4.5b. The screw dislocation
derives its name from the spiral or helical path or ramp that is traced around
the dislocation line by the atomic planes of atoms.

Figure 4.5 (a) A screw dislocation within a crystal. (b) The screw dislocation in (a)
as viewed from above. The dislocation line extends along line AB. Atom positions
above the slip plane are designated by open circles, those below by solid circles.
Mixed /partial dislocations
 Most dislocations found in crystalline materials are probably neither pure edge
nor pure screw but exhibit components of both types; these are termed mixed
dislocations.
 To add to the complexity of real defect structures, dislocation are often split in
"partial“ dislocations that have their cores spread out over a larger area.
INTERFACIAL DEFECTS
 Interfacial defects are boundaries that have two dimensions and normally
separate regions of the materials that have different crystal structures and/or
crystallographic orientations. These imperfections include external surfaces,
grain boundaries, phase boundaries, twin boundaries, and stacking faults.

External Surfaces
 Surface atoms are not bonded to the maximum number of nearest neighbors and
therefore they are in a higher energy state than the atoms at interior positions.
 The bonds of these surface atoms that are not satisfied give rise to a surface energy,
expressed in units of energy per unit area (J/m^2 or erg/cm^2).
 To reduce this energy, materials tend to minimize, if at all possible, the total surface
area.
 For example, liquids assume a shape having a minimum area—the droplets become
spherical. Of course, this is not possible with solids, which are mechanically rigid.
Grain Boundaries
 Polycrystalline material comprised of many small crystals or grains.
 The grains have different crystallographic orientation.
 There exist atomic mismatch within the regions where grains meet.
These regions are called grain Boundaries

 Grain boundaries Surfaces and interfaces are more chemically

reactive and impurities tend to segregate there. Since energy is
associated with interfaces, grains tend to grow in size at the expense
of smaller grains to minimize energy. This occurs by diffusion which is
accelerated at high temperatures.
 High and Low Angle Grain Boundaries
 Depending on misalignments of atomic planes between adjacent grains we
can distinguish between the low and high angle grain boundaries

When the orientation

mismatch is slight, on
the order of a few
degrees, then the term
small- (or low-) angle
grain boundary is used.

Figure 4.8 Schematic diagram showing small and high-angle grain boundaries and the adjacent atom positions.
Tilt and Twist Grain Boundaries
 Low angle grain boundary is an array of aligned edge dislocations. This
type of grain boundary is called tilt boundary (consider joint of two
wedges)

 Twist boundary - the boundary region consisting of arrays of screw

dislocations (consider joint of two halves of a cube and twist an angle
around the cross section normal)

Figure 4.9
Transmission electron
Demonstration of
microscope image of a
how a tilt
small angle tilt
boundary having
boundary in Si. The red
an angle of
lines mark the edge
misorientation
dislocations, the blue
results from an
lines indicate the tilt
alignment of edge
angle
dislocations
Twin Boundaries
 A twin boundary is a specific mirror lattice symmetry; that is, atoms on one side of
the boundary are located in mirror image positions to those of the atoms on the
other side.

 Low-energy twin boundaries with mirrored atomic positions across boundary

may be produced by deformation of materials. This gives rise to shape memory
metals, which can recover their original shape if heated to a high temperature.

 Shape-memory alloys are twinned and when deformed they untwin. At high
temperature the alloy returns back to the original twin configuration and restore
the original shape.

Figure 4.10 Schematic diagram showing

a twin plane or boundary and the adjacent
atom positions (colored circles).
 Twins result from atomic displacements that are produced from applied
mechanical shear forces (mechanical twins) and also during annealing heat
treatments following deformation (annealing twins).

 Twinning occurs on a definite crystallographic plane and in a specific direction,

both of which depend on the crystal structure.

 Annealing twins are typically found in metals that have the FCC crystal structure,
whereas mechanical twins are observed in BCC and HCP metals.

Phase Boundaries
 Phase boundaries exist in multiphase materials, in which a different phase exists
on each side of the boundary; furthermore, each of the constituent phases has
its own distinctive physical and/or chemical characteristics.
Bulk or Volume Defects
 Bulk defects are normally introduced during processing and fabrication
steps.
 Presence of volume defects can greatly affect electrical, mechanical,
thermal, and optical properties of the material
 Pores - can greatly affect optical, thermal, mechanical properties
 Cracks - can greatly affect mechanical properties
 Foreign inclusions - can greatly affect electrical, mechanical,
optical properties

A cluster of micro cracks in a

melanin granule irradiated by
a short laser pulse.
Stacking Fault
 Stacking fault is a an error in the staking sequence of planes in the
crystal.
 Stacking faults are found in FCC metals when there is an interruption in
the ABCABCABC . . . stacking sequence of close-packed planes

Here is Stacking
Bloch walls
 The ability of a ferromagnetic material (such as iron, nickel or iron

oxide) to be magnetized and demagnetized depends in large part on

the presence of two-dimensional imperfections known as Bloch walls.

 These interfaces are boundaries between two regions of the crystal

which have a different magnetic state.

 As magnetization occurs, these defects migrate and by their motion

provide the material with a net magnetic moment. Without the existence

of Bloch walls all ferromagnetic materials would be permanent

magnets. In fact, electromagnets would not exist if it were not for this

type of defect.
Atomic Vibrations

 Heat causes atoms to vibrate

 Vibration amplitude increases with temperature

 Melting occurs when vibrations are sufficient to rupture bonds

 Vibrational frequency ~ 10^13 Hz

 Average atomic energy due to thermal excitation is of order KBT

Basic Concepts Of Microscopy
 To examine the structural elements and defects that influence the properties of

materials.

 For investigation of the microstructural features of all material types.

 To study and characterization of materials.

Several important applications of microstructural examinations are as follows:

 To ensure that the associations between the properties and structure (and defects)

are properly understood,

 To predict the properties of materials once these relationships have been

established,

 To design alloys with new property combinations, to determine whether a material

has been correctly heat-treated, and to ascertain the mode of mechanical fracture.
Optical Microscopy

 The light microscope is used to study the microstructure; optical and

illumination systems are its basic elements.
 Used of light radiation.
 For materials that are opaque to visible light (all metals and many
ceramics and polymers), only the surface is subject to observation, and
the light microscope must be used in a reflecting mode.
 Careful and meticulous surface preparations are necessary to reveal the
important details of the microstructure.
 The specimen surface must first be ground and polished to a smooth and
mirror-like finish.
 This is accomplished by using successively finer abrasive papers and
powders and also using an appropriate chemical reagent in a procedure
termed etching to reveal the microstructures.
Figure (a) Polished and etched grains as they might appear when viewed with an
optical microscope. (b) Section taken through these grains showing how the etching
characteristics and resulting surface texture vary from grain to grain because of differences
in crystallographic orientation. (c) Photomicrograph of a polycrystalline brass specimen, 60.
Figure (a) Section of a grain boundary and its surface groove produced by etching;
the light reflection characteristics in the vicinity of the groove are also shown. (b)
Photomicrograph of the surface of a polished and etched polycrystalline specimen of an
iron–chromium alloy in which the grain boundaries appear dark, 100.
Electron Microscopy
 use electron beam at high kilowatt
 Needed for high magnification power to reveal internal structure.
 High magnifications and resolving powers of these microscopes are
consequences of the short wavelengths of electron beams.
 The electron beam is focused and the image formed with magnetic lenses;
otherwise, the geometry of the microscope components is essentially the
same as with optical systems.
. Transmission Electron Microscopy
 The image seen by TEM is formed by an electron beam that passes through
the specimen.
 Details of internal microstructural features are accessible to observation.
 a specimen to be examined must be prepared in the form of a very thin foil to
transmit electron easily.
 The transmitted beam is projected onto a fluorescent screen to be viewed.
 Magnifications approaching to 1,000,000.
Scanning Electron Microscopy
 The surface of a specimen to be examined is scanned with an electron

beam, and the reflected (or back-scattered) beam of electrons is collected

and then displayed on display board.

 The scanned image, represents the surface features of the specimen.

 The specimen must be electrically conductive; for nonconductive

specimen should be coated.

 Magnifications ranging from 10 to in excess of 50,000 are possible.

 Used to examine qualitative and semi quantitative analysis of the

elemental composition of very localized surface areas.

Grain-size Determination
 The grain size is often determined when the properties of polycrystalline
and single phase materials are under consideration
 In the earlier grain-size determinations were performed manually using
photomicrographs.
 However, today, most techniques are automated and use digital images
and image analyzers with the capacity to record, detect, and measure
accurately features of the grain structure (i.e., grain intercept counts,
grain boundary lengths, and grain areas).

Two Common Grain-size Determination Techniques

1. linear intercept—counting numbers of grain boundary intersections by
straight test lines; and
2. comparison—comparing grain structures with standardized charts,
which are based upon grain areas (i.e., number of grains per unit area).
For the linear intercept method,

1. lines are drawn randomly through several photomicrographs that show the

grain structure (all taken at the same magnification).

2. Grain boundaries intersected by all the line segments are counted. Let us

represent the sum of the total number of intersections as P and the total

length of all the lines by LT. The mean intercept length l [in real space (at

1x i.e., not magnified)], a measure of grain diameter, may be determined

by the following expression:

where M is the magnification

The comparison method
1. ASTM (American standard testing materials) has prepared several
standard comparison charts, all having different average grain sizes.

2. To each is assigned a number from 1 to 10, which is termed the grain size
number; the larger this number, the smaller the grains.

3. Let G represent the grain-size number, and let n be the average number of
grains per square inch at a magnification of 100 x.

4. These two parameters are related to each other through the expression.

Grain size no.

No. of grains/square inch

N = 2 G-1
 For photomicrographs taken at magnifications other than 100, use of the following

In this expression, nM is the number of grains

per square inch at magnification M..

Relationships have been developed that relate mean intercept length to ASTM grain-size
number; these are as follows:

To compute magnification from a scale bar, the following procedure may be used:
1. Measure the length of the scale bar in millimeters using a ruler.
2. Convert this length into microns [i.e., multiply the value in step (1) by 1000 because
there are 1000 microns in a millimeter].

Magnification M is
 Determining Grain Size, using a micrograph taken
at 300x
• We count 14 grains in a M 
2
G 1
NM    2
1 in2 area on the (300x)  100 
M is mag. of image
image
N M is measured grain count at M
• To report ASTM grain now solve for G:
size we needed a log( N M )  2  log  M   log 100    G  1 log  2 

measure of N at 100x 
log  N m   2log  M   4
not 300x G 1
log  2 
• We need a conversion log 14   2log 300   4
G  1  7.98  8
method! 0.301
For this same material, how many Grains would I
expect /in2 at 100x? At 50x?
G 1 81
N 2 2  128 grains/in (at 100x)
2

Now, how many grain would I expect at 50x?

2 2
 100 
8 1  100 
NM  2     128*  
 M   50 
N M  128* 2  512 grains/in
2 2
END
Issues To Address...
Review of Atomic Structure
• Electrons, Protons, Neutrons, Electron states,
The Periodic Table

Atomic Bonding in Solids

• Energies vs. Forces

Primary Interatomic Bonds

• Ionic, Covalent, Metallic

Secondary Bonding (Van der Waals)

Molecules and Molecular Solids
Atomic Structure
Atoms = nucleus (protons and neutrons) + electrons
Charges:
 Electrons (-): protons(+) (1.6 × 10-19 Coulombs).
 Neutrons are electrically neutral.
Masses:
 Protons and Neutrons (~1.67 × 10-27 kg).
 Electron (9.11 × 10-31 kg)
The atomic mass (A): total mass of protons + total mass of neutrons = Z+N
Atomic weight ~ Atomic mass , why not consider the electron mass as well?
Atomic number (Z) = is the number of protons per atoms
chemical identification of element
In neutral atom, Atomic number (Z) = # protons = # electrons
Isotope number  # neutrons, number of neutrons for an element can vary from the
number of protons (atoms of some elements have two or more different atomic masses).
This is called isotopes. AXZ , i.e. 1H1, 2H1, 3H1
The Atomic Mass Unit (amu) :
1 amu is defined as the 1/12 of the atomic mass of the most common
isotope of carbon, carbon 12 (12C6). Atomic mass of 12C6 is 12 amu :
Carbon= 6 protons (Z=6) + 6 neutrons (N=6)

Mproton ~ Mneutron = 1.67 x 10-24 g = 1 amu

The atomic weight A, Weighted average of atomic masses of naturally occurring

isotopes. A, is often expressed in mass per mole

A mole is the amount of matter that has a mass in grams equal to the atomic
mass in amu of the atoms (A mole of carbon has a mass of 12 grams).

 The number of atoms in a mole is called the Avogadro number,

 One Mole contains Avogadro’s number of atoms, Nav = 6.023 × 1023 atoms/mole

Nav = 1 gram/1 amu.

Example: Atomic weight of iron = 55.85 amu/atom = 55.85 g/mole
Some simple calculations
Calculating n, the number of atoms per cm3 of a material of density ρ (g/cm3):
n = Nav × ρ / A
Number density, n: (number of atoms per cm 3); Mass density, ρ (g/cm3); Atomic mass, A (g/mol):

Graphite (carbon): ρ = 2.3 g/cm3, A = 12 g/mol

n = 6×1023 atoms/mol × 2.3 g/cm3 / 12 g/mol
= 1.15 × 1023 atoms/cm3
Diamond (carbon): ρ = 3.5 g/cm3, A = 12 g/mol
n = 6×1023 atoms/mol × 3.5 g/cm3 / 12 g/mol
= 1.75 × 1023 atoms/cm3
Water (H2O) ρ = 1 g/cm3, A = 18 g/mol
n = 6×1023 molecules/mol × 1 g/cm3 / 18 g/mol
= 3.3 × 1022 molecules/cm3
SIZE of a Atom or Molecule
 If n = 6 × 1022 atoms/cm3 Mean separation between atoms L = (1/n)1/3 = 0.25 nm.
 Electrons in Atoms
ATOMIC MODELS

Towards the end of 19th century physicists realized Newtonian physics has serious
difficulty in explaining many phenomena involving electrons => quantum
mechanics
Bohr atomic model
 The electron is a particle which is assumed to
revolve around the atomic nucleus in discreet
circular orbits. Electron energy quantized into shells.
Wave mechanical model
 Electrons have wavelike and particle-like characteristics.
–This means that electrons are in orbitals.
–Electron position is defined in terms of a probability
distribution at various locations around the nucleus.
–Electron energy quantized into both shells and subshells
  Both models allow electrons to only be at particular energy levels: have

discrete energy states.

 Using wave mechanics: each orbital at discrete energy level is determined
by four parameters, called quantum numbers:
Quantum Numbers for Electrons
 n, l , ml , ms
N, principal quantum number, determine energy level or, distance of an
electron from the nucleus, K, L, M, N, O, ( N= 1, 2, 3,…..)
L, angular momentum quantum number, subshell, describes the
shape of the subshell, s, p, d, f, (L= 0, 1, 2, 3, …..n-1)
M, third or magnetic quantum number, number of energy states in

a subshell, determines orbital 1, 3, 5, 7 (M = -l to +l )

Ms, fourth quantum number, spin moment of electron ( +½, -½ )

nn --->
---> shell
shell 1,1,2,2,3,3,4,4,......
l l --->
---> subshell
subshell 0,0,1,1,2,2,......nn--11
mlml --->
---> orbital
orbital -l-l ......00......+l+l
mms ---> electron spin +1/2
+1/2and and-1/2
s ---> electron spin -1/2
 Conti.

2l+1

 Quantum numbers are the numbers that assign electrons in an atom to

discrete energy levels.
 Quantum shell is a set of fixed energy levels to which electrons belong.
 Quantum of energy is the amount of energy needed to move an electron from
one energy level to another energy level.
 Atomic Orbitals
• Different atomic orbitals are denoted by letters. The s orbitals are
spherical, and p orbitals are dumbbell-shaped.

• Four of the five d orbitals have the same shape but different
orientations in space.

• The seven f orbitals are

 Electron Configurations
 The ways in which electrons are arranged in various orbitals around
the nuclei of atoms are called electron configurations.
 The rules are:
• Aufbau Principle

– Electrons occupy the orbitals of lowest energy first. In the aufbau

diagram below, each box represents an atomic orbital.

• Pauli Exclusion Principle

– An atomic orbital may describe at most two electrons. To occupy

the same orbital, two electrons must have opposite spins; that is,

the electron spins must be paired.

• Hund’s Rule

– States that electrons occupy orbitals of the same energy in a way

that makes the number of electrons with the same spin direction

as large as possible.
Filling Diagram for Sublevels
Electronic Structure
 Electrons have wavelike and particulate properties.

 This means that electrons are in orbitals defined by a

probability.

 Each orbital at discrete energy level determined by quantum

numbers.

 Valence electrons are those that occupy the outermost shell.

These electrons are extremely important, they participate in the

bonding between atoms to form atomic and molecular aggregates.

 Valence electrons determine chemical, electrical, thermal and

optical properties etc.

 Electron Energy States
Electrons...
 Have discrete energy states (2,6,10,14)

 Tend to occupy lowest available energy state.

 Electrons fill levels in order of increasing energy (only n, 

make a significant difference).

 When all electrons are at the lowest possible energy levels

=> ground state

 Excited states do exist such as in glow discharges etc…

 Outermost shell – the valence electrons responsible for

bonding.
 The Periodic Table

 All the elements have been classified according to electron configuration

in the periodic table

 The element situated with increasing atomic number in seven horizontal

rows called periods.

 All the elements arrayed in 1 column or group have similar :

 valence electron
 chemical properties
 physical properties
 Conti.
• Elements in same column share similar properties.

• Group number  number of electrons available for bonding

• Inert gases (He, Ne, Ar...) filled subshells: chem. inactive

• Alkali metals (Li, Na, K…) one electron in outer shell eager to give up

electron – chem. active

• Halogens (F, Br, Cl...) missing one electron in outer shell - want to

gain electron - chem. Active

• Subshells with one electron - low electronegativity

• Subshells with one missing electron -high electronegativity

 Electropositive – can give up their few valence electrons to become positively
charged ions, i.e. Readily give up electrons to become + ions.
 Electronegativity - is the degree to which an atom attracts electrons to itself. i.e.
Readily acquire electrons to become - ions.
 Electronegativity increases across the period and decreases down the group.

Smaller electronegativity Larger electronegativity

 Atomic Bonding in Solids
BONDING FORCES AND ENERGIES

 Considering the interaction between two isolated atoms as they are

brought into close proximity from an infinite separation.
 At larger distances, the interactions are negligible.

 As the atoms approach, each exerts force on the other.

• Attractive
• Repulsive

• Attractive component is due to nature of the bonding (minimize energy thru

electronic configuration)
• Repulsive component is due to Pauli exclusion principle; electron clouds tend to
overlap.
• Essentially atoms either want to give up (transfer) or acquire (share) electrons
to complete electron configurations; to minimize their energy.
 Figure 2.10 (a) The
dependence of repulsive,
attractive, and net forces
on interatomic separation
for two isolated atoms.
(b) The dependence of
repulsive, attractive, and
net potential energies on
interatomic separation for
two isolated atoms.

E0 – bond energy
F= dE/dr
r0 –equilibrium distance
at r0, dE/da = 0,  Fa = Fr
• Bond is a force that holds groups of two or more atoms together and
makes them function as a unit.

• Bond energy (potential energy or bond strength): is the amount of

energy required to break a particular bond.

• Bond breakage is an endothermic process; bond energy is always
positive. Bond formation is an exothermic process
• Bond Length For a given pair of atoms, a higher bond order results in
a shorter bond length and a higher bond energy. A shorter bond is a
stronger bond.
• Bond order: the number of electron pairs being shared between any
two bonded atoms.
 The repulsive force dominates at small distances, and the attractive

force dominates at larger distances. At equilibrium they are just equal.

 The total energy has a minimum at the point of equilibrium separation.

Bonding energy E0 corresponds to the energy at ro– the energy that

would be required to separate these two atoms to an infinite separation.

 holding one atom at the origin, a second atom would repel that atom at

separation r < ro and attract it when ro< r.

 r0 is approximately 0.3 nm.

 The magnitude of this bonding energy and the shape of the energy–

versus–interatomic separation curve vary from material to material,

and they both depend on the type of atomic bonding.

 Furthermore, a number of material properties depend on E0, the

curve shape, and bonding type.

 Electron volt
• The electron volt (eV) Energy unit convenient for atomic
bonding
Electron volt –
energy lost/gained when an electron is taken
through a potential difference of one volt.

E=qV
For q = 1.6 x 10-19 Coulombs
V = 1 volt
1 eV = 1.6 x 10-19 J
 Primary Interatomic Bonds
 Primary Bonding: e- are transferred or shared.
 The transfer is strong (100-1000 KJ/mol or 1-10 eV/atom).
 Interionic energy can be defined as the energy needed to rip a
compound into its components placed infinitely far apart => (Enet (∞) = 0).

IONIC BONDING

 bond formed between two ions by the transfer of electrons.

 Strong Coulomb interaction between a positive atom (lost an
electron, Na+) and a negative atom (an extra electron, Cl)
 Occurs between + and – ions (anion and cation).
 Large difference in Electronegativity required.
 Ionic compounds result when metals react with nonmetals
Repulsive energy ER

Interatomic separation r

Net energy EN

Attractive energy EA
• Electron transfer reduces energy of the system
• Na shrinks and Cl expands

• Oppositely charged ions attract, attractive force is coulombic.

• Ionic bond is non-directional, ions get attracted to one another in any direction.
• Bonding energies are high => 2 to 5 eV/atom, molecule, ion
General properties of ionic compounds
Strong electrostatic attraction => High melting and evaporation points, hard
and brittle solids at room temperature electrical and thermal insulator.
COVALENT BOND
 Generally it forms between nonmetallic elements of similar electro
negativity. Valence electrons spend more time between nuclei than outside 
bonding.
 bond formed by the sharing of electrons.
 Bonds in all the polyatomic ions and diatomic are all covalent bonds
 Highly directional in direction of greatest orbital overlap.
 Stable non-ionizing particles, they are not conductors at any state.

 Examples; O2, CO2, C2H6, H2O, SiC, H2 , Diamond, boron nitride,

quartz (SiO2).
Covalent Solids

 Hard and incompressible

 Non volatile Diamond
(each C atom has four
 insoluble covalent bonds with four
other carbon atoms)
graphite
A covalent bond is a balance of attractive and repulsive forces.

HA + HB HA HB

NONPOLAR COVALENT BONDS

 when electrons are shared equally

H2 or Cl2
POLAR COVALENT BONDS

 when electrons are shared but shared unequally

H2O • water is a polar molecule because oxygen is more

electronegative than hydrogen, and therefore
electrons are pulled closer to oxygen.
Metallic Bonding
 bond found in metals and its alloys; holds metal atoms
together very strongly
 Valence electrons are detached from atoms Spread in an
'electron sea' that "glues" the “ions” together.
 Metallic bond is non-directional  atoms pack closely
 Metals are shinny.
 Workability.

Metals Form Alloys

 Metals do not combine with metals.
They form Alloys which is a solution of a metal in a metal.
Examples are steel, brass, bronze.
Intermolecular Forces
Secondary Bonding
 Secondary bond is a physical bond which is very weak.

 Secondary bonding exists between virtually all atoms or molecules,

but its presence may be obscured if any of the three primary bonding
types is present.

 Secondary bonding forces arise from atomic or molecular dipoles.

 The bonding results from the coulombic attraction between the

positive end of one dipole and the negative region of an adjacent one.

 polar molecules: e.g. HCl, H2O

=> Due to asymmetry of positive and negative regions. it is
strongest
Polar molecule induces a dipole in adjacent non-polar molecule. =>
Attraction between the permanent and induced dipoles. Exist by virtue of
an asymmetrical arrangement of positively and negatively charged
regions (HCl)

Mutual dipoles induced (vander Waals) => This bond is the weakest (He-
He, H2 - H2).

Fluctuating Induced Dipole Bonds: A dipole may be created or induced

in an atom or molecule that is normally electrically symmetric i.e.
Fluctuations of electron density distribution in one atom is felt by the
electrons of an adjacent atom. The attraction force temporally fluctuate
with time (H2, Cl2).
2

Permanent Dipole Bonds: Coulombic forces also exist between adjacent

polar molecules (HF, H2O, NH3).
Example: hydrogen bond in water. The H end of the molecule is
positively charged and can bond to the negative side of another H 2O

molecule (the O side of the H2O dipole)

Hydrogen bonding in liquid water

from a molecular-level simulation

“Hydrogen bond” – secondary bond formed between two

permanent dipoles in adjacent water molecules.
 MIXED BONDING

 For many real materials, the atomic bonds are mixtures of two
or more of mixed bonds.

 The four bonding types—ionic,

covalent,
metallic, and vander Waals—on what is
called a bonding tetrahedron

Examples of bonding in Materials:

 Metals: Metallic
 Ceramics: Ionic / Covalent
 Polymers: Covalent and Secondary
 Semiconductors: Covalent or Covalent / Ionic
 Percent ionic character (%IC) of a bond between elements A and B (A
being the most electronegative) may be approximated by the
expression

where XA and XB are the electro negativities for the respective elements.

Determine the characters of the bond, the tendency to ionic or covalent bond.

Molecules
Molecules: Primary bonds is inside, and secondary bonds among each other

Many common molecules are composed of groups of atoms bound

together by strong covalent bonds, including elemental diatomic
molecules (F2, O2, H2, etc.), as well as a host of compounds (H2O,
CO2, HNO3, C6H6, CH4, etc.).
Bond Formation
 A bond can result from a “head-to-head” overlap of atomic
orbital's on neighboring atoms.

Overlap of H (1s) and Cl (2p)

 This type of overlap places bonding electrons in a Molecular

orbital along the line between the two atoms and forms Sigma
bond (s).

Sigma Bond Formation by Orbital Overlap

 Two s Atomic Orbital's (A.O.s) overlap to form an s (sigma)
Similarly,
Molecular Orbital (M.O.)   two p A.O.s
H H can overlap
• + • •  • end-on to
 from a p
sigma bond ( ) M.O.
Summary
END