Properties of Materials

Types of Stresses

F
Tensile

F
Compressive

Bending

F
F

Shear

Stress vs Strain

force
area
length
strain
length
stress

Representative Stressstrain curves

Youngs Modulus (E)

The slope of the stress-strain
curve in the elastic region.
Hookes law: E = /
A measure of the stiffness of
the material.
Larger the value of E, the
more resistant a material is to
deformation.
Note: ET = Eo bTe-To/T
where Eo and b are empirical
constants, T and To are
temperatures

Units:
E: [GPa] or [psi]
: dimensionless

Stress-Strain Behavior (summary)

Elastic deformation
Reversible:
( For small strains)
Stress removed material returns to original size

Plastic deformation
Irreversible:
Stress removed material does not return to
original dimensions.
Yield Strength ( y)

The stress at which plastic deformation becomes

noticeable (0.2% offset).

P the stress that divides the elastic and plastic

behavior of the material.

True Stress & True Strain

True stress = F/A
True strain = ln(l/l0)
= ln (A0/A)
(A must be used after
necking)

Engineering stress

F
A0

Engineering strain

l l0
l0

Apparent softening
L

True Strain t

dl

ln

Lo

True Stress t
AL A o Lo

t ln 1
t 1

Load
A

L
Lo

Load
A0

Toughness
The total area under the true stress-strain curve which
measures the energy absorbed by the specimen in the
process of breaking.

Toughness

Tensile properties: Ductility

The total elongation of the specimen due to plastic deformation, neglecting

the elastic stretching (the broken ends snap back and separate after failure).

Textbooks
Essentials of Materials Science & Engineering
Second Edition
Authors: Donald R. Askeland & Pradeep P. Fulay
Materials Science and Engineering: An Introduction
Sixth Edition, Author: William D. Callister, Jr.
The Science and Engineering of Materials
Fourth Edition, Authors: Askeland and Phule
(Fulay ?)
Introduction to Materials Science for Engineers
Sixth Edition, Author: James F. Shackelford

SUMMARY
Stress and strain: These are size-independent
measures of load and displacement, respectively.
Elastic behavior: This reversible behavior often
shows a linear relation between stress and strain.
To minimize deformation, select a material with a
large elastic modulus (E or G).
Plastic behavior: This permanent deformation
behavior occurs when the tensile (or compressive)
uniaxial stress reaches y.
Toughness: The energy needed to break a unit
volume of material.
Ductility: The plastic strain at failure.
Note: materials selection is critically related
to mechanical behavior for design
applications.

Viscoelastic Behavior
Polymers have unique mechanical properties vs. metals & ceramics.
Why?
Bonding, structure, configurations
Polymers and inorganic glasses exhibit viscoelastic behavior
(time and temperature dependant behavior)
Polymers may act as an elastic solid or a viscous liquid
i.e. Silly Putty (silicon rubber)
- bounces, stretches, will flatten over long times

resilient rubber ball

Elastic behavior rapid deformation

Low Strain Rate

High extension - failure

Very low Strain rate - Flatten

Flow like a viscous fluid

Polymers
Polymer : Materials are made up of many (poly) identical chemical units
(mers) that are joined together to construct giant molecules.
Plastics - deformable, composed of polymers plus additives. E.g. a variety
of films, coatings, fibers, adhesives, and foams. Most are distinguished by
their chemical form and composition.
The properties of polymers is related to their structures, which in turn,
depend upon the chemical composition. Many of these molecules contain
backbones of carbon atoms, they are usually called "organic" molecules
and the chemistry of their formation is taught as organic chemistry.
The most common types of polymers are lightweight, disposable, materials
for use at low temperatures. Many of these are recyclable. But polymers are
also used in textile fibers, non-stick or chemically resistant coatings,
adhesive fastenings, bulletproof windows and vests, and so on.

Polymers
Polymer : Materials are made up of many (poly)
identical chemical units (mers) that are joined together
2
to
construct
giant
Carbon
1s22s
2p2 molecules.
It has four electrons in its outermost shell, and needs four more to
make a complete stable orbital. It does this by forming covalent
bonds, up to 4 of which can be formed.
The bonds can be either single bonds, ie one electron donated by
each participating element, or double bonds (2 e- from each), or
triple bonds (3 from each)
2
2

X4

C
X4

X1

X4

X1

X4

Xi can be any entity ex H, O, another C, or even a similar monomer

Polymers many repeating units

X2
X4

C
X4

X2
X1

X4

X1

X4

C C C C C
And so on if the bonds can keep getting formed, entire string-like
structures (strands, or chains) of the repeating units are created. C
is the most common element in polymers. Occasionally, Si may

Classes of Polymers
Thermoplastics:
Consist of flexible linear molecular chains
that are tangled together like a plate of
spaghetti or bucket of worms. They
soften when heated.
Thermosets:
Remain rigid when heated & usually
consist of a highly cross-linked, 3D
network.
Elastomers:
Consist of linear polymer chains that are
lightly cross-linked. Stretching an
elastomer
causes
chains toare
partially
Of all the
materials,
polymers
perhaps the most versatile,
untangle
but not
permanently
not only
because
thedeform
properties
can be drastically modified
the thermoplastics).
by simple (like
chemistry,
but the behavior is also dependent on
the architecture of the chains themselves.
From proteins to bullet-proof jackets to bottles, polymers are

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

Illustration

backbon
e

side-group

a) & b) 3 dimensional
models,

c) Is a simpler 2-D

Chain Conformations

Polymer Synthesis - I

Addition
in which one mer is
added to the structure at
a time.
This process is begun by
an initiator that "opens
up" a C=C double bond,
attaches itself to one of
the
resulting
single
bonds, & leaves the
second one dangling to
repeat the process

Polymer Synthesis - II

Condensation
in which the ends of
the
precursor
molecules lose atoms
to form water or
alcohol,
leaving
bonds that join with
each other to form
bits of the final large
molecules.
An
example is shown in
the
Detail
the
formation of nylon.

Molecular weight
distribution

The degree of polymerization (DP) = no. of monomers per polymer. It is

determined from the ratio of the average molecular weight Mw of the polymer
to the molecular weight of the repeat unit (MRP).
DP = Mw / MRP
where
Mw = fi Mi : Mw = weight average molecular weight
Mn = xi Mi : Mn = number average molecular weight
Mi = mean molecular weight of each range
fi = weight fraction of polymer having chains within that range
xi = fraction of total number of chains within each range

Molecular Weight Distributions

Mn

x M
i

Mw

w M x M
i

xi

2
i

ni

number fraction
i

Degree of Polymerization
Mn
M
; nw w
m
m
m "mer" molecular weight

nn

Degree of polymerization &

Degree of polymerization (DP)- number of monomers per polymer
molecular weight
chain, ie no. of repeat units.
Obviously, the weight (either in AMU, or in g/mol) is the same for
each repeat unit. Then, the total weight of the polymer chain, ie
its molecular weight is :mol. Wt. = N.Mm
where N is the number of monomers in that chain, ie the
DP;
Mm is the weight of the monomer.
In a polymer sample synthesized from monomers by either
condensation or addition polymerization, one always has a
distribution of DPs amongst the resulting chains.
So let us consider that we have 100 monomers. Let the weight of
each monomer be 1g/mol (in reality, this is Hydrogen !) Let us see
some ways in which we can arrange this:
1)1 chain of N=100, ie mol. Wt. = 100
2)2 chains of N=50 each, ie mol. Wt. = 50

Degree of polymerization &

3 chains, 2 of N=25, and 1 of N=50.
molecular weight
Now, to calculate the average molecular weight, we have

two

methods:
1) Take the simple numerical average, ie
(25+25+50)/3.0 = (2x25 + 1x50)/3.0 = 33.33. This value is
according to the number fraction of each type of chain (1/3 of
the chains are of N=50, and 2/3 have N = 25)
2) Take the average according to the weight fraction of each
chain. What is the total weight ?
Mtotal=100
Wfraction50 = 50/100, ie , Wfraction25=2*25/100 = 1/2
So, taking weight fractions, we get the average molecular
weight as
Mw = 50*1/2 + 25*1/2 = 25+12.5 = 37.5
So, numerical fractions, and weight fractions for mol. Wt. give
different answers!
Mn = SUM(niMi)/Sum(ni) , where ni = no. of chains of length Mi
Mw = SUM(wiMi), where wi = weight fraction of chains of length M i.

Degree of polymerization &

Suppose we want to find out the average population of each
molecular weight
state.*
We can go to each senator of each state and find out what the
population of their state is, and then divide that number by
100.
This number is the number-average population for each state.
This is exactly similar to the Mn that we calculated earlier, ie
no. av. Mol. wt.. Problem ?
Yes, of course. What do we do about say, CA and AK ?
Now, senators are busy, so we ask congressmen from each state.
Then,
we
take
the
value
that
each
congressman/congresswoman gives us, and then divide by
the number of congresscritters. What value do we get ?
Certainly one different from our earlier attempt ! Problem ?
Now the value is much higher than before. This is exactly similar
to the Mw that we calculated earlier, ie to weight av. mol. Wt.
Is this value MUCH more representative (eh eh !) of the average
population of each state ? Well, not really. But at least, it is an

Polymer Architecture
Polymer = many mers
mer
H H H H H H
C C C C C C
H H H H H H

Polyethylene (PE)

mer
H H H H H H
C C C C C C
H Cl H Cl H Cl

mer
H H H H H H
C C C C C C
H CH 3 H CH3 H CH 3

Polyvinyl chloride (PVC)

Polypropylene (PP)

Covalent chain configurations and strength:

secondary
bonding

Linear

Branched

Cross-Linked

Direction of increasing strength

Network

Polymer Architecture - II
Structure of polymers strongly affects their properties; e.g., the ability of
chains to slide past each other (breaking Van der Waals bonds) or to arrange
themselves in regular crystalline patterns.
Some of the parameters are: the extent of branching of the linear polymers;
the arrangement of side groups. A regular arrangement (isotactic) permits
the greatest regularity of packing and bonding, while an alternating pattern
(syndiotactic) or a random pattern (atactic) produces poorer packing
which lowers strength & melting temperature.

Isomerism different structures, but same chemical composition

H H H H H H H H H H

Isotactic

C
C

C
C

C
C

C
C

R H R H R H R H R H
H H H H H H H H H H

Syndiotactic

C
C

C
C

C
C

C
C

R H H R R H H R R H
H H H H H H H H H H

Atactic

C
C

C
C

C
C

C
C

R H H R R H R H R H

Stereoisomerism

Cant Crystallize

Polymer Architecture SchematicsIf you have

some
red beads and
some black beads,
how can you make
polymers out of
them ?

Rando
m

Block
y

Alternati
ng

Branched

Polymer Architecture - III

We have discussed polymers comprised of a single kind of
a monomer, ie just one repeating entity. However, this is
not unique: we can synthesize polymers that consist of
different repeating units, and such polymers are called
copolymers
The combination of different mers allows flexibility in
selecting properties, but the way in which the mers are
combined is also important. Two different mers can be
alternating, random, or in blocks along the backbone
or grafted on as branches.

Thermoplastic &
Thermosetting Polymers
Thermoplastics:
--little cross-linking
--ductile
--soften w/heating
Ex: grocery bags, bottles
Thermosets:
--large cross-linking
(10 to 50% of mers)
--hard and brittle
--do NOT soften w/heating
--vulcanized rubber,
epoxies,
polyester resin, phenolic
resin
Ex: car tyres, structural
crossplastics

Vulcanization
In thermoset, the network is inter-connnected in a non-regular fashion. Elastomers
belong to the first category. Polyisoprene, the hydrocarbon that constitutes raw natural
rubber, is an example. It contains unsaturated C=C bonds, and when vulcanizing rubber,
sulfur is added to promote crosslinks. Two S atoms are required to fully saturate a pair
of C=C bonds and link a pair of adjacent molecules (mers) as indicated in the
reaction.
Without vulcanization, rubber is soft and sticky and flows viscously even at room
temperature. By crosslinking about 10% of the sites, the rubber attains mechanical
stability while preserving its flexibility. Hard rubber materials contain even greater sulfur
additions.

Vulcanization

Molecular weight,
Crystallinity and
Molecular weight M : Mass of a mole of chains.
Properties
w

smaller M
w

larger Mw
Tensile strength (TS):
--often increases with Mw.
--Why? Longer chains are entangled (anchored) better.
% Crystallinity: % of material that is crystalline.
--TS and E often increase
with % crystallinity.
crystalline
--Annealing causes
region
crystalline regions
amorphous
to grow. % crystallinity region
increases.

Semicrystalline Polymers

Oriented chains with long-range ord

Amorphous disordered polymer chai

the intercrystalline region
~10 nm spacing

Mechanical Properties of Polymers

Elasticity of Polymers
Random arrangement = High Entropy

Stretched = Low Entropy

py is a measure of randomness: The more ordered the chains are, the lo

entropy. Spontaneous processes always tend to increase the entropy, w
ns that after stretching, the chains will tend to return to a high-entropy st

Viscosity of Polymers
Low entropy state

Elastic Deformation

creep
Slow Deformation

random

Cross-linking stops the sliding of chains

VISCOELASTIC RESPONSE
Elastic

Viscoelastic

Viscous

Viscoelasticity: T Dependence
Temperature & Strain Dependence:
Low T & high strain rates = rigid
solids
High T & low strain rates = viscous

Modulus of elasticity

Thermoplastic (uncrosslinked) medium times Rubber-like Elasti

Deformation
Glassy (Elastic-high modulus)
Leathery
(Elastic-low modulus)
Rubbery Plateau
Elastic at high strain rate
Long times
Viscous at low strain rate

Tg

Temp.

Tm

Slow
relaxation

Heavy Crosslinking
Elastomer
Light crosslinking
Branched polymer
Thermoplastic
No crosslinking
Tg

Crosslinked

Tm

Log Mod. Of Elasticity

Log Mod. Of Elasticity

Viscoelasticity: Structure
Effect of crosslinking
Effect of crystallinity
Dependence
Thermoset
100 % crystalline

50 % Crystalline
amorphous

Tg

Branched

Tm

Crystals act like crosslinks

Strain Induced Crystallization in N

TENSILE RESPONSE: ELASTOMER

(ex: rubberband)
(MPa)
60 xbrittle failure
plastic failure

40

20
0
0
initial: amorphous chains are
kinked, heavily cross-linked.

elastomer

final: chains
are straight,
still
cross-linked

Deformation
is reversible!

Compare to responses of other polymers:

--brittle response (aligned, cross linked & networked

case)

T & STRAIN RATE: THERMOPLASTICS

(ex: plastic bottles or containers)

Decreasing T...

--increases E
--increases TS
--decreases %EL
Increasing
strain rate...

--same effects
as decreasing T.

(MPa)
80 4C
60
40

20C

Data for the

semicrystalline
polymer: PMMA
(Plexiglas)

40C

20
0
0

60C
0.1

0.2

to 1.3
0.3

TIME-DEPENDENT DEFORMATION
Stress relaxation test:

--strain to and hold.

--observe decrease in
stress with time.
tensile test

strain
(t)
time

Relaxation modulus:

(t)
E r (t)
o

Data:

Large drop in Er
for T >

105
E r (10s)
3
10
in MPa
101

(amorphous
polystyrene)
T g.

rigid solid
(small relax)
transition
region

10-1

viscous liquid
10-3 (large relax)

60 100 140 180T(C)

Tg

Relaxation Modulus

Log Relaxation Modulus

Time-Temperature
Lo
T
Superposition

Hi T
Log Time

Stress,

Relaxation Modulus

Glass-like elasticity
Rubber-like
elasticity

10

Fluid-like
Viscous
10 s

time

Viscoelsticmodulus

fixed

Modulus of elasticity E r (10s) =

L
Lo

RelaxationModulus

Er(0)= E, Youngs Modulus

Er( )= 0

(10)
fixed