01213211

MATERIALS SCIENCE
FOR ENGINEERS

STRUCTURE OF MATERIALS

Department of Materials Engineering

Faculty of Engineering
Kasetsart University
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Periodic table
All elements are classified in the periodic table

2
 Classification of Materials
• Composed of one or more
metallic elements
• Fe, Al, Cu, Ti, Au, and Ni

• Compound between
metallic and nonmetallic
element, or between
nonmetallic elements
• Oxides : Al2O3, SiO29 10616072in
• Nitrides : Si3N4
• Carbides : SiC ] ñ¥tN
• Organic compound that are chemically
Composites based on carbon, hydrogen, and other
• Formed from two or more nonmetallic elements
materials (metal, ceramic,
polymer), producing properties • Plastic and rubber
not found in any single material
3
Applications

4
Applications

5
Case Study : Materials for
carbonated beverage container
Carbonated beverage = a beverage that
has had carbon dioxide dissolved into it
Materials property requirements for the
containers
Nontoxic, unreactive with the beverage,
recyclable
Relatively strong
Inexpensive, including the cost to produce
Be capable of being produced in different
color and/or decorated with the decorative
label
Provide a barrier to the passage of CO2 in
the container
If optically transparent, the container can
retain its optical clarity

6
Case Study : Materials for
carbonated beverage container
Aluminum (metal)
Pros
Nontoxic and unreactive with the beverage
Relatively strong
Good barrier to CO2 diffusion
Cool beverage rapidly
Allow label to be painted on the surface
Cons
Opaque and relatively expensive to produce
Easily dented

7
Case Study : Materials for
carbonated beverage container
Glass (Ceramic)
Pros
Nontoxic and unreactive with the beverage
Relatively inexpensive materials
Good barrier to CO2 diffusion
Can be recycled
Optically transparent
Cons
Crack and fracture easily
Relatively heavy

8
Case Study : Materials for
carbonated beverage container
Plastic (Polymer)
Pros
Nontoxic and unreactive with the
beverage
Relatively strong
Can be made optically transparent
Inexpensive and lightweight
Can be recycled
Cons
Not as impervious to the passage of CO2
as the aluminum and glass
9
Case Study: Then & Now
Many of the scientific problems that are faced today are due to the limitations of the materials that
are available and, as a result, breakthroughs in the field of materials science & engineering are
likely to have a significant impact on the future of technology.

128MB 128GB
$107.99(2014)

19 mm

16 hours of Full HD
video, 7,500 songs, 2GB
1994 vs. 2014 3,200 photos and more 10
than 125 apps $99(2006)
Democritus (460‐370 BCE)
John Dalton (1766‐1844)

Atomic Structure
The atomic number (Z) of an element is equal to the number of protons in
the nucleus.
The atomic mass (A) of a specific atom is the sum of the masses of protons
and neutrons within the nucleus.
Valence electrons are the electrons that occupy the outermost filled shell.

11
Chemical Bond
Primary Bonds - involving the transfer or sharing of
valence electrons
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Ionic
Covalent cotton
Secondary Bonds - involving the attraction forces
between molecules
Van der Waals Bond
Hydrogen Bond

12
Chemical Bond
Metallic bond - the positively charged ion cores are
shielded from one another, and also "glued" together by
the sea of valence electrons
• primary bond for metals and
sea of valence  
electrons their alloys
• Metallic bond solid
• good electrical and thermal
conductor

13
Chemical Bond
Ionic bond - electrostatic attraction between oppositely
charged ions
Found in compounds that are composed of metal and
nonmetal elements
General properties of ionic materials : strong, brittle
materials with high melting temperatures compared to
metal, electrical insulator (no free electrons)

14
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Chemical Bond

Covalent bond - electron sharing

between two adjacent atoms such
Carbon atom
that each atom assumes a stable
electron configuration
Covalently Bonded Solids :
Diamond
Properties
High melting temperature
Very hard solid Diamond
Cutting Wheel
Electrical conductivity is very poor
because of no free electrons.
15
Chemical Bond
→ Em
Electronegativity
a relative measure of the ability of an atom to attract
the electrons in a bond it forms with another atom.
Ionic bond
created between two unlike atoms with large
different electronegativities
Covalent bond
Created between atoms having comparable
electronegativities

16
Chemical Bond

17
Chemical Bond
Secondary Bonds – Van der Waal bonding
Involve attraction forces between molecules
No transfer or sharing of electrons in secondary bonding
Bonds are weaker than primary bonds

18
Chemical Bond
Secondary Bonds – Hydrogen bond
- A weak type of force that forms a special type
of dipole-dipole attraction
- Occurs when a hydrogen atom bonded to a
strongly electronegative atom exists in the
vicinity of another electronegative atom with a
lone pair of electrons.
- Generally stronger than ordinary dipole-dipole
and dispersion forces, but weaker than
covalent and ionic bonds.

19
20
pious Ñbi=Ñhn µ%ow=Ñw
Crystalline and Amorphous Solid
1%7 In
union ↑
Crystalline materials: 11nF

Materials at which their atoms are

arranged orderly.
Metals, alloys, many ceramics
Amorphous materials:
Materials at which their atoms are
arranged randomly.
Silicate glass, some polymer
Semicrystalline = ↓
Crystalline + Amorphous Trainor
Polymer
21
Case Study : Water
Solid Ice
• Crystalline structure
• For each molecule, 4 nearest -neighbor
molecules
• Relatively open structure
• Lower density than liquid water
• Upon freezing, volume increase by 9%

Liquid Water
• Crystalline structure is destroyed
• Water molecules become more closely
packed together
• At room temperature, each molecule
has 4.5 nearest -neighbor molecules

22
Example: Water
• Consequence of freezing phenomenon

Floating Ice Break up of theroad

pavement due tofreeze
and thawcycle
Antifreezecoolant
• Prevent engineblock  
from cracking by  
water freezing

23
Crystalline Solid
Single Crystal Materials
Periodic arrangement of
atoms extends throughout
the entirety of the material
without interruption
19 rai ng
Polycrystalline materials
comprised of many individual
grains or crystallites.
Each grain can be considered
-
as a single crystal, within
which the atomic structure has
long-range order.
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Crystalline Solid
Grain

25
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Concept of Unit Cell
-

Unit cell
the smallest repeating 
unit having the full 
symmetry of the crystal 
structure.

26
Crystal Structures in Solids
Lattice, Lattice Points, Unit Cell
Unit Cell = basic structural  
unit or building block of  
the crystal structurewhich  
has the characteristics  
similar to the entire lattice

Lattice Point
= 1 atom (Metal)
= 1 group of atoms(Ceramic)
Ex
Lattice = Collection points   Buckminsterfullerene
arranged in periodicorder (C60)
27
Crystal Structures
Lattice Parameters
Numbers describing size and shape of a unit cell-
6 numbers: a, b, c, , ,

90o  90o

90o 90
o  

90o

90o 90
o
y
90o

x
28
 The seven crystal systems (unit cell geometries)
http://catalog.flatworldknowledge.com/bookhub/4309?e=averill_1.0‐ch12_s02 29
30
 ""
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Cubic Unit Cell
↑
¥:{ ¥

= BCC FCC

31
http://www.chem.ufl.edu/~itl/2045/lectures/lec_h.html
 Cubic Unit Cell
• Model that shows the portion of each atom that lies within the
unit cell, and an aggregate of several unit cells

http://catalog.flatworldknowledge.com/bookhub/4309?e=averill_1.0‐ch12_s02
32
Crystal Structures
Number of atoms per unit cell

1 atom/cell ½ atom/cell

1/8 atom/cell
33
Crystal Structures
Number of atoms per unit cell

34
 Crystal Structures
Coordination Number
Numbers of nearest neighbor atoms for a particular atom

SC BCC FCC
Coordination Number = 6 Coordination Number = 8 Coordination Number = 12

35
 Crystal Structures
Lattice Parameter vs. Atomic Radius

a a 4R
R

4 4
R
SC: a 2R BCC: a R FCC: a
3 2

36
Crystal Structures •
Atomic Packing Factor (APF)
Fraction of space occupied by atoms

APF
Volume of Atoms in an Unit Cell
Volume of an Unit Cell •
Example: APF of SC
volume of an unit cell a3 (2r) 3 8r 3
4 3
volume of an atom r
3
4 3
1 r
atom/unit cell volume / atom 3
APF 0.52
1 atom / unit cell volume / unit cell 8r 3

37
 96 On cell

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Crystal Structures
Close-Packed Structure
Atomic Packing Factor (APF)
-

a a 4R
R

APF = 0.52 APF = 0.68 APF = 0.74

main 4¥
• Close-Packed Structure
• The possible highest packing factor with atoms of one size
38
Crystal Structures
Hexagonal Close Packed (HCP) Crystal Structure

• APF = 0.74 • c/a = 1.633

• C.N. = 12 • 2 atoms/unit cell 39
Crystal Structures of Metals

40
 Crystal Structures of Metals
Bcc = his Nik
Summary Fcc = luw% iinmiw •
Hcp = works
i.

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41
☆
a
Theoretical Density ( ) ••
• Density determination from a single unit cell

Weight of Atoms in an Unit Cell A

Volume of an Unit Cell NV
where = density (g/cm3), A = sum of atomic weights of all the atoms in an unit cell,  
N = Avogadro’s number, and V = volume of an unit cell (cm3)

• By inserting the value of N = 6.02 × 1023

A A A
NV 6.02 1023 V 10 21
602V
where  = density (g/cm3), and V’ = unit cell volume in nm3
42
Example
Iron (Fe) has a BCC crystal structure, an atomic radius of 0.124 nm, and an  
atomic weight of 55.85 g/mol. Compute its theoretical density

A • 2 atoms / Unit Cell
From

602V • and 3a 4R

A Number of Fe atoms in an Unit Cell Atomic Weight of Fe

2 55.85 111.7
3 3
4 4
V a3 R 0.124 nm
3 3
A 111.7
3
7.90 g cm3 (Experimental Value = 7.87 g/cm3)
602V 4
602 0.124 nm 43
3
 Case Study: Tin
• Consequences of structural transformation
• Volume increase by 27 %
Tetragonal

• Decrease in density from 7.30 g/cm3 to

5.77 g/cm3
• Volume expansion results in the
disintegration of the white tin metal into
13.2 oC  
the gray coarse powder
Cooling
Cubic

44
45
 Crystal Structures of Ceramics
Ceramic
More complex than metal

• Rocksalt Crystal • Cesium Chloride • Zinc Blende

Structure Crystal Structure Crystal Structure
46
Crystal Structures of Ceramics
Factors that determine crystal structure
Relative sizes of ions – formation of stable structures:
maximize the number of oppositely charged ion neighbors
(Coordination number)

Maintenance of Charge Neutrality :

Net charge in ceramic should be zero. 47
Crystal Structures of Ceramics

48
Crystal Structures of Ceramics

c
49
Crystal Structures of Ceramics

50
Non-crystalline Structure: Ceramic
• Depends on the ease with which a random atomic structure in the liquid can
transform to an ordered structure during solidification
4-
Crystalline structure of SiO2 SiO4 tetrahedron

Amorphous structure of SiO2

Quartz crystal cluster

Fused Quartz Labware 51
Case Study: Carbon

52
Example: Carbon

53
X-Ray Diffraction
X-ray = an electromagnetic radiation having high
energies and short wavelength
When a beam of x-rays impinges on a solid material,
the beam will be scattered
Bragg’s Law

reflections must
be in phasefor
a detectable signal
extra  
distance  
travelled  
by wave“2” spacing
d between
planes
54
X-Ray Diffraction
X-ray Diffractometer = an instrument used to
measure the intensity of the outgoing x-ray
from the specimen and determine the angle
at which the diffraction occur (outgoing x-
rays are in phase)

X‐Ray   Detector
Source

Specimen  
Stage

55
X-Ray Diffraction
Diffraction pattern

56
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Applications
Phase identification
Ex: Check the composition
of the raw materials for
making cement
Determination of structural
properties
atomic spacing, theoretical
density, crystallinity of ÷:*
polymers
Analysis of residual stress
Texture analysis " " " "iw

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g. 57
Imperfections in Solids
Point Defects
Vacancies and Self-
Interstitials
Vacancy
the missing of an
atom
Self-Interstitial
An atom from the
crystal move to an
interstitial site
Less chance to
occur than vacancy
58
Imperfections in Solids
Impurity (1) Substitutional (2) Interstitial
Alloys
Impurity atoms are added to a metal to improve their properties

Substitutional
Impurity atoms replace
the host atoms

Interstitial
Impurity atoms fill the
voids among the host
atoms
59
Imperfections in Solids
Point defects in Ceramic
Frenkel defect - A pair of point
defects produced when an ion
moves to create an interstitial
site, leaving behind a
vacancy.
Schottky defect - A point
defect in ionically bonded
materials. In order to maintain
a neutral charge, a
stoichiometric number of
cation and anion vacancies
must form.
# Na+ vacancies : # Cl- vacancies = 1:1
60
 Imperfections in Solids
Dislocation – one dimensional defect
(1) Edge Dislocation and (2) Screw Dislocation
(1) Edge Dislocation → eñnoeo Hsiao
-

An edge dislocation is a defect where an extra half-plane of atoms is

introduced mid way through the crystal, distorting nearby planes of
atoms.

The perfect crystal is cut and an extra half plane of atom is inserted
61
 Imperfections in Solids
(2) Screw Dislocation
Upper part shifted one atomic distance

The perfect crystal is cut and sheared one atom spacing 62

Imperfections in Solids
Mixed Dislocation
Edge Dislocation + Screw Dislocation

• TEM (Transmission Electron

Microscope) image of dislocation
• Normally taken at 50,000 to
300,000 times 63
Imperfections in Solids
Dislocation
Motion

64
Imperfections in Solids
Interfacial Defects
External Surface Phase Boundaries
Grain Boundaries
Only 8 nearest neighbors
External Surface surface
Atoms at the  
surface have the  
12 nearest neighbors
nearest neighbors  
less than theatoms  
inside 65
Imperfections in Solids
Grain Boundary
Polycrystalline materials
Boundary separating two  
small crystals having  
different crystallographic  
Grain orientations in  
polycrystalline materials
Atomic mismatch within  
the boundary due to the  
change in crystalline  
orientation 66
Imperfections in Solids
Phase Boundary
Change in organization of molecules

67
Imperfections in Solids
Bulk or Volume Defect
Crack, pores
Atomic Vibrations
Every atom in a solid material is vibrating very rapidly
about its lattice position within the crystal

68
 Microscopy
• A technical field of using microscopes to view samples and objects that  
cannot be seen with the unaided eye

69
 Microscopy
• Length scale

70
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TEM
,
Microscopy
Microscopes are instruments designed to produce
magnified visual or photographic images of small
objects.

Optical Microscope (OM) Electron Microscope (EM)

(Light Microscope) 71
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The light microscope is used to study the microstructure.

Only the surface is subject to observation and the light
microscope must be used in a reflecting mode.
Useful up to 2,000X
=

magnification
Investigations of this type
are often termed
metallographic,
since metals were first
examined using this
technique.
72
 Specimens Preparation
ASTM Standard E3-01: Guide for Preparation of
Metallographic Specimens
(ASTM = American Society for Testing and Materials)

Grinding Polishing Etching

• Polishing removes surface
features (e.g., scratches)
• Involves the use of loose
abrasive (e.g. oxide slurry),
on a cloth-covered
electrically powered wheel
• Applying the solution (acid or base ) on the
surface of the specimen
• Grain boundaries are more susceptible to
etching and may be revealed as dark lines

• Rubbing specimen on
stationary sand paper or
holding the specimen against
the rotating wheel covered
with the sand paper Read more at 73
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Scanning Electron Microscope (SEM)
Uses electrons to illuminate a sample
At each location where the electron beam
strikes the sample, the electron signals
from the specimen are used to produce the
image.
Magnifications ranging from
10x to 300,000x (conventional SEM)

74
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 Scanning Electron Microscope
(SEM)
Energy dispersive x-ray spectrometer (EDS/EDX)
Accessory equipment permits qualitative and quantitative
analysis of the elemental composition of very localized
surface areas.
http://www.umich.edu/~ocm/tools/ups.html

EDS

http://serc.carleton.edu/research_educat 
ion/geochemsheets/eds.html

• An energy dispersive x-ray spectrometer mounted to scanning electron microscope

• This instrument allows for elemental analysis of the samples 75
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76
Scanning Electron Microscope (SEM)
Sample : Filler (Glass fiber) in Resin
Accelerating Voltage : 1.0 kV
Magnification : 1,000x
Sample : Titanium Oxide Particle
Accelerating Voltage :3 kV
Magnification : 15,000x
Sample : Courtesy of Prof. Masato
Kakihana, Tohoku University
77
 11516dg
p
Scanning Electron Microscope (SEM)

78
Scanning Electron Microscope (SEM)

Tick Fly Eye

79
 Jozwiak
/ www.wkiannlutor t-i inynoib
: Transmission Electron
Microscope (TEM)
John The electron beam is actually passed
Twain through a specimen
The specimen must be very thin, with a
thickness of less than 100 nm
Magnifications approaching 20,000,000X
are possible (ref: http://www.globalsino.com/EM/ )
6

Troponin

Lattice defects
of CdTe 80
Transmission Electron Microscope (TEM)

81
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Scanning Probe Microscopy 1

a branch of microscopy that forms images of surfaces ☆afvwÑnW

using a physical probe that scans the specimen ↳ low
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An image of the surface is obtained by mechanically
moving the probe in a raster scan of the specimen, line =
by line, and recording the probe-surface interaction as a {
function of position =mm%
High resolution atomic resolution possible

Atomic Force Microscopy (AFM)
Scanning Tunnelling Microscopy (STM)
Magnetic Force Microscopy (MFM)
Near‐field Scanning Optical Microscopy (NSOM)
82
 Atomic Force Microscope (AFM)
The displacement of the tip is monitored using a laser spot bounced off the
back of the cantilever and imaged on a photodiode array

A schematic illustration of an
atomic force microscope
connected to a computer.
83
Atomic Force Microscope (AFM)

84
 Atomic Force Microscope (AFM)

Atomic force microscope

image of the surface of
spider silk
85
Images from Various Microscopes
Scanning Electron  
Microscope (SEM)
A. Sewing needle
B. Human hair
D. Bacterial cell
Transmission Electron  
Microscope (TEM)
C. Mammalian cell
E. Herpes viruses
F. Enzyme molecules
Scanning Probe  
Microscopy (SPM)
G. Point defect ingraphite

86
Polymeric Materials in Everyday Life

87
Definition of polymer
MONOMER
mono = one meros = part

POLYMER (Greek root)

poly = many meros = part

“substance containing high-molecular-weight molecules,

consisting of repeating unit which are bond to each other”

88
Example : Polyethylene

89
 C wive

or feels
Bonding of polymer chains
Primary bonding: Covalent interatomic bonds:

*Sharing of electrons between adjacent atoms

- single bonds : saturated hydrocarbons
- double and triple bonds : unsaturated hydrocarbons

Secondary bonding:

*Intermolecular van der Waals forces

*Intermolecular hydrogen bonding

90
 Useful facts about polymer
macromolecule composes of the hydrocarbon molecule
(H and C)
the backbone of a string of carbon atoms, long and
flexible chains, which covalent interatomic bonds
chain-like molecules having molecular weights from
10,000 to more than 1,000,000 g/mole
monomer is a starting material, usually small molecule,
from which polymers are created.
polymerization – The process by which small molecules
are joined to form polymers.

91
Elements in Polymers

Besides carbon and

Hydrogen, the
following atoms may
be incorporated in
polymer molecules:
Oxygen, Nitrogen,
chorine, fluorine,
silicon,
phosphorous, and
sulfur.

92
Example of polymer molecules

93
Spectroscopy → 001am ÑbnnW
=

Spectroscopy is the measurement of the absorption or

emission of energy by matter (atoms or molecules)
when it is subjected to electromagnetic radiation.
A spectrophotometer measures the energy changes
that take place within a molecule when it is irradiated
and records these changes as spectra .
In absorption spectroscopy , molecules absorb energy
and undergo transitions from the ground state to an
excited state of the molecule.
The type of spectroscopy involved will depend on the
region of the electromagnetic spectrum that is used as
a radiation source.
94
95
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Infrared Spectroscopy ( IR )

• A beam of infrared radiation is passed FTIR Spectrophotometer

through the sample 100
• A similar beam is passed through the

% Transmittance
reference cell
• The frequency of radiation is varied
• Bonds vibrating with a similar frequency
absorb the radiation
• The amount of radiation absorbed by the 0
sample is compared with the reference 4000 Wavenumber (cm-1) 400
• The results are collected, stored and

irouxÑWhV
plotted FTIR spectrum
→ µ 96
 Polymer Structure
Polymer structures are divided into two main categories—
amorphous and semi-crystalline—based on their difference in
molecular arrangement.

(1) Amorphous structure: (2) Semi‐crystalline structure: mixtures of ordered  

disordered molecular arrangement. and disordered moleculararrangements.

97
 Crystallinity of Polymer

Lamella

• Chain-folded model - chains fold back and forth

– is a model for semi-crystalline structure of
polymers
• The crystalline regions take the form of thin
platelets (crystallites) in which the chains are
aligned perpendicular to the flat faces of the
platelets and folded repeatedly
• During solidification, many platelets grow out
from a central nucleus into larger structures
called spherulites. Spherulite
• Each spherulite consists of many smaller
crystallites separated by thin amorphous regions.
98
 Crystallinity of Polymer
Atomic arrangement in polymer crystals is more complex than in metals or
ceramics (unit cells are typically large and complex).

Figure 15.16 Photograph of spherulitic  
crystals in an amorphous matrixof
nylon ( 200). (From R. Brick, A. Pense  
and R. Gordon, Structure and  
Properties of Engineering Materials,  
4th Ed., McGraw‐Hill, 1977.)

99
Molecular structure
The physical characteristics of polymer material depend not only on
molecular weight and shape, but also on molecular structure:

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1) Linear polymers 2) Branched polymers
‐mer units joined end toend in   –side‐branched chains connected to
singlechains main ones
‐long, ‘straight’, flexible chains   –considered to be part of themain  
with some van der Waals or   chain molecule
hydrogen bonding between   –results from side reactionsthat  
chains. occur during synthesis
Examples: polyethylene, nylon. – chain packing efficiency is reduced,
lowers polymerdensity
– polymers that form linear
Dept of Mat Eng structures may also bebranched 100
Molecular structure

G.
uns

3) Crosslinked polymers 4) Network polymers

–adjacent linear chainsstrongly –3‐dimensional networks,  
joined to because mer units have 3active  
one another covalent bonds – tri‐functional
–achieved during synthesis or by a   –a highly crosslinked polymer  
non‐reversible chemical reaction may also be considered as a  
–often accomplished byadditive   network polymer
atoms or molecules that are   –materials have distinctive  
covalently bonded to thechains mechanical and thermal  
–many rubber elastic materials are   properties
crosslinked, called vulcanisation Examples: epoxies, phenol‐
formaldehyde
Dept of Mat Eng 101