Chapter 2

Overview on Basic
Materials Properties

Reference: William F. Smith, Javad Hashemi, 2006,

Foundations of Materials Science and Engineering,
4th ed., McGraw-Hill

Only for Teaching

Materials Categories
Metallic Materials
---Inorganic and have crystalline structure.
---Good thermal and electric conductors.

Polymeric (Plastic) Materials

Organic giant molecules and mostly noncrystalline.

Some are mixtures of crystalline and noncrystalline regions.
Poor conductors of electricity and hence used as insulators.
Strength and ductility vary greatly.
Low densities and decomposition temperatures.

Examples :- Poly vinyl Chloride (PVC), Polyester.

Applications :- Appliances, DVDs, Fabrics etc.

Materials Categories
Ceramic Materials
Metallic and nonmetallic elements are chemically
bonded together.
Inorganic but can be either crystalline, noncrystalline
or mixture of both.
High hardness, strength and wear resistance.
Very good insulator. Hence used for furnace lining for
heat treating and melting metals.
Also used in space shuttle to insulate it during exit and
reentry into atmosphere.
Other applications : Abrasives, construction materials,
utensils etc.
Example:- Porcelain, Glass, Silicon nitride.

Materials Categories
Composite Materials
Mixture of two or more materials.
Consists of a filler material and a binding material.
Materials only bond, will not dissolve in each other.
Mainly two types :---Fibrous: Fibers in a matrix
---Particulate: Particles in a matrix
---Matrix can be metals, ceramic or polymer
Examples : Fiber Glass ( Reinforcing material in a polyester or
epoxy matrix)
Concrete ( Gravels or steel rods reinforced in cement
and sand)
Applications:- Aircraft wings and engine, construction.

Materials Categories

Electronic Materials
Not Major by volume but very important.
Silicon is a common electronic material.
Its electrical characteristics are changed by adding impurities.

Examples:- Silicon chips, transistors

Applications :- Computers, Integrated Circuits, Satellites etc.

Space Lattice & Unit Cells

Atoms, arranged in repetitive 3-Dimensional pattern, in long range

order (LRO) give rise to crystal structure.
Properties of solids depends upon crystal structure and bonding
force.
An imaginary network of lines, with atoms at intersection of lines,
representing the arrangement of atoms is called space lattice.
Space Lattice

Unit cell is that block of

atoms which repeats itself
to form space lattice.
Materials arranged in
short range order are
called amorphous materials
Unit Cell

Crystal Systems and Bravais Lattice

Only seven different types of unit cells are

necessary to create all point lattices.
According to Bravais (1811-1863) fourteen
standard unit cells can describe all possible lattice
networks.
The four basic types of unit cells are
Simple

Body Centered
Face Centered
Base Centered

Unit Cells

Cubic Unit Cell

a=b=c
= = = 90

Simple

Body Centered

Face centered

Tetragonal
a =b c
= = = 90

Simple

Body Centered

Ref: W.G. Moffatt, G.W. Pearsall, & J. Wulff,

The Structure and Properties of Materials, vol. I: Structure, Wiley, 1964, p.47.)

Unit Cells

Orthorhombic
a b c
= = = 90
Simple

Face Centered

Base Centered

Body Centered

Rhombohedral
a =b = c
= = 90

Simple

Unit Cells

Hexagonal
a = b =a c

= = 900, = 1200

Simple

Monoclinic
a b c

Base
Centered

= = 900, 900
Simple

Triclinic
a b c

900
Simple

10

Direction Indices

Determine direction indices of the given vector.

Origin coordinates are (3/4 , 0 , 1/4).
Emergence coordinates are (1/4, 1/2, 1/2).
Subtracting origin coordinates
from emergence coordinates,
(3/4 , 0 , 1/4) - (1/4, 1/2, 1/2)
= (-1/2, 1/2, 1/4)
Multiply by 4 to convert all
fractions to integers
4 x (-1/2, 1/2, 1/4) = (-2, 2, 1)
Therefore, the direction indices are [ 2 2 1 ]

11

Miller Indices

Miller Indices are used to refer to specific lattice

planes of atoms.
They are reciprocals of the fractional intercepts (with
fractions cleared) that the plane makes with the
crystallographic x,y and z axes of three nonparallel
edges of the cubic unit cell.
Miller Indices =(111)

12

Polymorphism or Allotropy

Metals exist in more than one crystalline form. This is

called polymorphism () or allotropy ().
Temperature and pressure leads to change in crystalline
forms.
Example:- Iron exists in both BCC and FCC form
depending on the temperature.
Liquid
Iron

9120C

-2730C

Iron
BCC

13940C 15390C

Iron
FCC

Iron
BCC
13

X-Ray Diffraction

Crystal planes of target metal act as

mirrors reflecting X-ray beam.

If rays leaving a set of planes

are out of phase (as in case of
arbitrary angle of incidence)
no reinforced beam is
produced.

If rays leaving are in phase,

reinforced beams are
produced.

14

XRD

For rays reflected from different planes to be in phase, the extra

distance traveled by a ray should be a integral multiple of wave
length .

n = MP + PN

(n = 1,2)

n is order of diffraction
If dhkl is interplanar distance,
Then MP = PN = dhkl.Sin
Therefore,

= 2 dhkl.Sin

Ref: A.G. Guy and J.J. Hren, Elements of Physical Metallurgy, 3d ed., Addison-Wesley, 1974, p.201.)

15

Example of XRD

= 2 dhkl.Sin

H-Y Chang et al, Nanotechnology 14 (2003) 603608

16

Substitutional Solid Solution

Solute atoms substitute for parent solvent atom in a

crystal lattice.
The structure remains unchanged.
Lattice might get slightly distorted due to change in
diameter of the atoms.
Solute percentage in solvent
can vary from fraction of a
percentage to 100%

Solvent atoms
Solute atoms

17

Substitutional Solid Solution

The solubility of solids is greater if

The diameter of atoms not differ by more than 15%

Crystal structures are similar.

No much difference in electronegativity (else compounds
will be formed).
Have some valence.

Examples:System

ElectroSolid
Atomic
negativity Solubility
radius
Difference difference

Cu-Zn

3.9%

0.1

38.3%

Cu-Pb

36.7%

0.2

0.17%

Cu-Ni

2.3%

100%
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Interstitial Solid Solution

Solute atoms fit in between the voids (interstices) of

solvent atoms.
Solvent atoms in this case should be much larger than
solute atoms.
Example:- between 912 and 13940C, interstitial solid
solution of carbon in iron (FCC) is formed.
A maximum of 2.8%
of carbon can dissolve
interstitially in iron.

Iron atoms r=0.129nm

Carbon atoms r=0.075nm

19

Crystalline Imperfections

No crystal is perfect.
Imperfections affect mechanical properties,
chemical properties and electrical properties.
Imperfections can be classified as
Zero dimension point defects.

One dimension / line defects (dislocations).

Two dimension defects (planar defects).
Three dimension defects (cracks).

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Point Defects Vacancy

Vacancy is formed due to a missing atom.

Vacancy is formed (one in 10000 atoms)
during crystallization or mobility of atoms.
Energy of formation is 1 eV.
Mobility of vacancy results in cluster of
vacancies.
Also caused due to
plastic deformation,
rapid cooling or particle
bombardment.

Figure: Vacancies moving to form vacancy cluster

21

Point Defects - Interstitially

Atom in a crystal, sometimes, occupies interstitial site.
This does not occur naturally.
Can be induced by irradiation.
This defects caused structural distortion.

22

Point Defects in Ionic Crystals

Complex as electric neutrality has to be maintained.

If two oppositely charged particles are missing, cationanion divacancy is created. This is Schottky imperfection.
Frenkel imperfection is created when cation moves to
interstitial site.
Impurity atoms are
also considered as
point defects.

23

Dislocations
Line Defects (Dislocations)
Edge Dislocation--Screw Dislocation--Mixed Dislocation---

24

Grain Boundaries (GB)

Grain boundaries separate grains.

Formed due to simultaneously growing crystals
meeting each other.
Width = 2-5 atomic diameters.
Some atoms in grain boundaries have higher energy.
Restrict plastic flow and prevent dislocation movement.

3D view of
grains

Grain Boundaries
In 1018 steel

(ref:A.G. Guy, Essentials of materials Science, McGraw-Hill, 1976.)

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Planar Defects
Grain boundaries, twins, low/high angle
boundaries, twists and stacking faults
Free surface is also a defect : Bonded to
atoms on only one side and hence has
higher state of energy Highly reactive
Nanomaterials have small clusters of
atoms and hence are highly reactive.

26

Atomic Diffusion in Solids

Diffusion is a process by which a matter is

transported through another matter.

Examples:
---Movement of smoke particles in air : Very fast.
---Movement of dye in water : Relatively slow.
---Solid state reactions : Very restricted movement due
to bonding.

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Diffusion mechanism

Atoms diffuse in solids if

Vacancies or other crystal defects are present

There is enough activation energy

Atoms move into the vacancies present.

More vacancies are created at higher temperature.

Diffusion rate is higher at high temperatures.

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Substitutional Diffusion

Example: If atom A
has sufficient activation
energy, it moves into the
vacancy self diffusion.

Activation
Energy of
Self diffusion

Activation
Energy to
form a
Vacancy

Activation
+ Energy to
move a
vacancy

As the melting point increases, activation energy also

increases
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Interstitial Diffusion mechanism

Atoms move from one

interstitial site to another.
The atoms that move must
be much smaller than the
matrix atom.
Example:
Carbon interstitially
diffuses into BCC or FCC
iron.

Interstitial atoms
Matrix
atoms

30

Steady State Diffusion

There is no change in concentration of solute atoms at
different planes in a system, over a period of time.
No chemical reaction occurs. Only net flow of atoms.
C1

Solute atom flow

Concentration
Of diffusing C
2
atoms

Distance x

Diffusing
atoms

Unit
Area

Net flow of atoms

Per unit area per
Unit time = J
31

Ficks First Law

The flux or flow of atoms is given by

J = D

dc

J = Flux or net flow of atoms.

D = Diffusion coefficient.

dx

dc

= Concentration Gradient.

dx

i.e. for steady state diffusion condition, the net flow of

atoms by atomic diffusion is equal to diffusion D times
the diffusion gradient dc/dx .

Example: Diffusivity of FCC iron at 500oC is 5 x 10-15

m2/s and at 1000oC is 3 x 10-11 m2/s

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Diffusivity

Diffusivity depends upon

Type of diffusion : Whether the diffusion is

interstitial or substitutional.
Temperature: As the temperature increases
diffusivity increases.
Type of crystal structure: BCC crystal has lower
APF than FCC and hence has higher diffusivity.
Type of crystal imperfection: More open
structures (grain boundaries) increases diffusion.
The concentration of diffusing species: Higher
concentrations of diffusing solute atoms will affect
diffusivity.

33

Non-Steady State Diffusion

Concentration of solute atoms at any point in metal
changes with time in this case.
Ficks second law:- Rate of compositional change is
equal to diffusivity times the rate of change of
concentration gradient.
Plane 2
Plane 1

d dc x
D

=
dt
dx dx

dC x

Change of concentration of solute

Atoms with change in time in different planes
34

Ficks Second Law

x
= erf
2 D
C s C0
t

Cs C x

Cs = Surface concentration of
element in gas diffusing
into the surface.
C0 = Initial uniform concentration
of element in solid.
Cx = Concentration of element at
distance x from surface at
time t1.
x = distance from surface
D = diffusivity of solute
t = time.

Cs
Time = t2
Time= t1

Cx

Time = t0
C0

Distance x

35

Phase Diagrams
Phase: A region in a material that differs in structure
and function from other regions.
Phase diagrams:
Represents phases present in metal at different conditions
(Temperature, pressure and composition).
Indicates equilibrium solid solubility of one element in
another.
Indicates temperature range under which solidification
occurs.
Indicates temperature at which different phases start to
melt.

36

Phase Diagram of Pure Substances

Pure substance exist as solid, liquid and vapor.

Phases are separated by phase boundaries.
Example : Water, Pure Iron.

Different phases coexist at triple point.

Ref: W. G. Moffatt, et al., The Structure and Properties of Materials, vol I: Structure, Wiley, 1965, p.151

37

Phase Rule

P+F = C+2 P = number of phases that coexist in a system

C = Number of components
F = Degrees of freedom

For pure water, at triple point, 3 phases coexist.

There is one component (water) in the system.
Therefore 3 + F = 1 + 2
F = 0.
Degrees of freedom indicate number of variables that
can be changed without changing number of phases.

38

Phase Diagram from Cooling Curves

Series of cooling curves at different metal composition

are first constructed.
Points of change of slope of cooling curves (thermal
arrests) are noted and phase diagram is constructed.
More the number of cooling curves, more accurate is
the phase diagram.

39

The Lever Rule

The Lever rule gives the weight % of phases in any

two phase regions.
Wt fraction of solid phase
= X s = w0 w 1
ws w1
Wt fraction of liquid phase
= X 1 = ws w 0
ws w1

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Iron Carbide Phase Diagram

Plain carbon steel: 0.03% to 1.2% C, 0.25 to 1% Mn and

other impurities.
Ferrite: Very low solubility
of carbon. Max 0.02 % at 7230C
and 0.005% at 00C.
Austenite: Interstitial solid
solution of carbon in
iron. Solubility of C is
2.08% at 11480C and 0.8%
at 00C.
Cementite: Intermetallic compound.
6.67% C and 93.3% Fe.

41

Binary Eutectic Alloy System

In some binary alloy systems, components have limited

solid solubility.
Example : Pb-Sn alloy.
Eutectic composition freezes
at lower temperature than all
other compositions.
This lowest temperature is
called eutectic temperature.

Eutectic temperature

Liquid

Cooling

solid solution + solid solution

42

Intermediate Phases and Compounds

Terminal phases:
Phases occur at the end
of phase diagrams.
Intermediate phases:
Phases occur in a
composition range inside
phase diagram.
Examples: Cu-Zn
diagram has both
terminal and
intermediate phases.
Five invariant peritectic
points and one eutectic
point.

43

Intermediate Phases in Ceramics

In Al2O2 SiO2 system, an intermediate phase called

Mullite is formed, which includes the compound
3Al2O3.2SiO2.

Ref: A. G. Guy, Essentials of Materials Science, McGraw-Hill, 1976

44

Ternary Phase Diagrams

Three components
Constructed by using a equilateral triangle ()
as base.
Pure components at each
end of triangle.
Binary alloy composition
represented on edges.
Temperature can be
represented as uniform
throughout the
Whole Diagram ----Isothermal section.

45

Ternary Phase Diagram

Example:- Iron-Chromium-Nickel phase diagrams.

Isothermal reaction at 6500C
for this system
Composition of any metal
at any point on the phase
diagram can be found by
drawing perpendicular
from pure metal corner to
opposite side and calculating
the % length of line at that
point

Ref: Metals Handbook, vol. 8: American Society of Metals, 1973, p. 425.

46

Ceramics

Ceramics are inorganic and nonmetallic.

Bounded by ionic or covalent bonds.

Good electrical and heat insulation property.
Brittle, and lesser ductility and toughness than
metals.
High chemical stability and high melting
temperature.
Traditional Ceramics: Basic components (Clay and
Silica).
Engineering Ceramics: Pure compounds (Al2O3,
SiC).

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Zinc Blende (ZnS) Crystal Structure

Four zinc and four sulfur atoms.

One type (Zn or S) occupies lattice points and another

occupies interstitial sites of FCC unit cell.
S Atoms
(0,0,0) ( , ,0) ( , 0, ) (0, , )
Zn Atoms
( , , ) ( , , )( ,, ) ( , , )
Tetrahedrally covalently bonded
(87% covalent character) with
CN = 8.
CdS, InAs, InSb and ZnSe have
similar structures.

ref: W. D. Kingery, H. K. Bowen, D. R. Uhlmann, Introduction to Ceramics,2nd ed., Wiley, 1976

48

Important Crystal Structures

Perovskite (CaTiO3) : Ca2+ and O2- ions form FCC unit

cell.
Ca2+ Ions occupy corners
O2- Ions occupy face centers.
Ti4+ ions are at octahedral
sites.
Graphite : Polymorphic form
of compound.
Layered structure with carbon
atoms in hexagonal arrays.
Good lubricating properties.

Ref: W. D. Kingery, H. K. Bowen, D. R. Uhlmann, Introduction to Ceramics,2nd ed., Wiley, 1976.

49

Silicate Structures
Silicate (SiO44-) is building block of silicates.

50% ionic and 50% covalent.

Many different silicate structures
can be produced.
Island structure: Positive ions
bond with the oxygen of SiO44tetrahedron.
Chain/ring structure: Two
corners of each SiO44- tetrahedron
bonds with corners of other
tetrahedron.

Ref: M. Eisenstadt, Mechanical properties of Materials, Macmillan, 1971, p.82.

50

Sheet Structures of Silicates

Sheet structure: Three corners of same planes of silicate

tetrahedron bonded to the corners of three other silicate
tetrahedra.
Each tetrahedron has one
unbounded oxygen and hence
chains can bond with other
type of sheets.
If the bondings are weak,
sheets slide over each other
easily.

Ref: M. Eisenstadt, Mechanical properties of Materials, Macmillan, 1971, p.83.

51

Silicate Networks
Silica: All four corners of the SiO44- tetrahedra share

oxygen atoms.
Basic structures: Quartz, tridymite and cristobalite.
Important compound
of many ceramic and
glasses.
Feldspars: Infinite 3D
networks.
Some Al3+ Ions replace
Si4+ Ions
Net negative charge.
Alkaline and alkaline fit into interstitial sites.
.

Ref: W. D. Kingery, H. K. Bowen, D. R. Uhlmann, Introduction to Ceramics,2nd ed., Wiley, 1976

52

Traditional Ceramics
Made up of clay, silica and feldspar.

Clay: Provide workability and hardness.

Silica: Provide better temperature resistance and MP.
Potash Feldspar: Makes glass when ceramic is fired.
SEM of Porcelain

Quartz
grain

Source: F. Norton, Elements of Ceramics, 2nd ed., Addision-Wesley,1974, p.140

High-silica
glass

53

Engineering Ceramics

Alumina (Al2O3): Aluminum oxide is doped with

magnesium oxide, cold pressed and sintered.
Uniform structure. Used for electric applications.

Silicon Nitride (Si3N4): Compact of silicon powder is

nitrided in a flow of nitrogen gas.
Moderate strength and used for parts of advanced engines.

Silicon Carbide (SiC): Very hard refractory carbide,

sintered at 21000C.
Used as reinforcement in composite materials.

Zirconia (ZrO2): Polymorphic and is subject to cracking.

Combined with 9% MgO to produce ceramic with high
fracture toughness.

54

Electrical Properties

Basic properties of dielectric:

Dielectric constant:Q = CV
Q = Charge
V = Voltage
C = Capacitance
C = 0A/d
0 = permittivity of free space
= 8.854 x 10-12 F/m
When the medium is not free space
C = K0A/d Where K is dielectric constant of the
material between the plates
55

Dielectric Strength and Loss Factor

Dielectric strength is measure of ability of material to hold

energy at high voltage.
Defined as voltage gradient at which failure occurs.
Measured in volts/mil. 1 mil=(1/1000) in=25 m
Dielectric loss factor: Current leads voltage by 90 degrees
when a loss free dielectric is between plates of capacitor.
When real dielectric is used, current leads voltage by 900
where is dielectric loss angle.
Dielectric loss factor = K tan
measure of electric
energy lost.

56

Ceramic Materials for Capacitors

Ceramics are used as dielectric materials for capacitors.

Example: Disk ceramic capacitors.

BaTiO3 + additive
Very high dielectric
constant
Used in ceramic based
thick film hybrid
electronic circuit
Higher capacitance per unit area

57

Ceramic Semiconductors

Ceramics can be used as semiconducting materials.

Thermistor: Thermally sensitive resistor.

NTC thermistor: Conductivity raises with temperature.
Solid solution oxides of Mn, Ni, Fe, Co and Cu are used to
obtain necessary property ranges.
By combining low conducting metal oxide with low
conducting oxides intermediate properties are obtained.
Example: Conductivity of Fe3O4 is reduced gradually by
adding increasing amounts in solid solution of MgCr2O4

58

Thermal Properties of Ceramics

Low thermal conductivity and high heat

resistance.
Many compounds are used as industrial
refractories.
For insulating refractories, porosity is desirable.
Dense refractories have low porosity and high
resistance to corrosion and errosion.
Aluminum oxide and MgO are expensive and
difficult to form and hence not used as refractories.

59

Insulation for Space Shuttle Orbital

About 70% of external surface is protected from heat by

24000 ceramic tiles.
Material: Silica fiber compound.
Density is 4kg/ft3 and withstands temperature up to 12600C.

60

Oxidation Reduction Reactions

A metal (e.g. Zn) placed in HCl undergoes corrosion.

Zn + 2HCl
ZnCl2 + H2
or
Zn + 2H+
Zn2+ + H2
also
Zn
Zn 2+ + 2e- (oxidation half cell reaction)
2H+ + 2eH2 (Reduction half cell reaction)
Oxidation reaction: Metals form ions at local anode.
Reduction reaction: Metal is reduced in local charge at
Local cathode.
Oxidation and reduction takes place at same rate.

61

Macroscopic Galvanic Cells with 1M Electrolyte

Two dissimilar metal electrodes immersed in

solution of their own ions.
Electrode that has more
negative oxidation potential
will be oxidized.
Zn
Zn2+, Cu2+
Cu
Half cell reactions are
Zn
Zn 2+ + 2e- E0 = -0.763 V
Cu
Cu2+ + 2e- E0 = + 0.337 V
Or Cu2+ + 2eCu E0 = -0.337 V (negative sign)
Adding two reactions,
Zn + Cu2+
Zn2+ + Cu E0cell = -1.1V

62

Galvanic Cells With Electrolytes not 1M

If the concentration of electrolyte surrounding anode is

not 1 molar, driving force for corrosion is greater.
There will be more negative emf half cell reaction
M
Mn+ + ne Nernst Equation:

E=E +
0

0.0592
n

log Cion
E = Net emf of half cell
E0 = Standard emf of half cell
n = Number of electrons transferred
Cion = Molar concentration of ions.

63

Galvanic Cells With Acid or Alkaline Electrolytes

Consider iron and copper electrodes in acidic electrolyte.

Since standard electrode potential of Fe to oxidize is

0.44 , compared to 0.337 of copper,
Fe
Fe2+ + 2e-

Since there are no copper ions to reduce

2H+ + 2eH2
If electrolyte contains oxidizing agent
O2 + 4H+ + 4e2H2O
If electrolyte is neutral or basic,
O2 + 2H2O + 4e4OH-

Ref: J. Wulff et al., The Structure and Properties of Materials, vol. II, Wiley, 1964, p.164.

64

Grain Grain boundary Electrochemical cells

Grain boundaries are more anodic and hence get corroded

by electrochemical attack.
Grain boundaries are at higher energy.
Impurities migrate to grain boundaries.
Solute segregation might cause grain boundaries to
become more cathodic.
Grain
Boundary
Grain boundary
(anode)

Grain boundary
(cathode)
anode

Cartridge Brass

65