Properties of Materials

Vikram K. Kuppa

Energy & Materials Engineering Program

SEEBME
University of Cincinnati

866 ERC
Ph: 513-556-2059
Vikram.kuppa@uc.edu
www.uc.edu/~kuppavm

Office Hours: MWF 10-11AM

 Types of Stresses

F F F F
Tensile Compressive

Bending
F
F
Shear
 Stress vs Strain

force
stress
area
length
strain
length
Representative Stress-strain
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
F
True stress = F/A Engineerin g stress
A0
True strain = ln(l/l0)
= ln (A0/A) l l0
Engineerin g strain
(A must be used after l0
necking)
Apparent softening

l
dl L
True Strain t ln
Lo
Lo

Load Load
True Stress t
A A0
AL A o Lo
t ln 1
t 1
 Toughness
The total area under the true stress-strain curve which
measures the energy absorbed by the specimen in the
process of breaking.

Toughness d
 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 Low Strain Rate Very low Strain rate - Flatten
Elastic behavior rapid deformation High extension - failure 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 to construct giant molecules.
Carbon 1s22s22p2
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)
X2 X2

X4 C X1 X4 C X1

X4 X4
Xi can be any entity ex H, O, another C, or even a similar monomer
 Polymers many repeating units
X2 X2

X4 C X1 + X4 C X1 +

X4 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 also participate in such bonding.
 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
to partially untangle but not deform permanently
(like the thermoplastics).
Of all the materials, polymers are perhaps the most versatile, not only because the
properties can be drastically modified by simple chemistry, but the behavior is also
dependent on the architecture of the chains themselves.
From proteins to bullet-proof jackets to bottles, polymers are INDISPENSIBLE to life
as we know it
 2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

Illustration

backbone

side-group

a) & b) 3 dimensional models,

c) Is a simpler 2-D representation
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 i
i

Mw w M x M i i i
2
i
i i
ni
xi number fraction
n i
i

Degreeof Polymerization
M M
nn n ; n w w
m m
m "mer" molecular weight

Degree of polymerization & molecular weight
Degree of polymerization (DP)- number of monomers per polymer 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
3) 10 chains of N=10 each, ie mol. Wt. = 10
4) 3 chains, 2 of N=25, and 1 of N=50
Degree of polymerization & molecular weight
3 chains, 2 of N=25, and 1 of N=50.
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 Mi.

But, wi = niMi/SUM(niMi) ie the weight of that polymer (i), divided by total

weight.
So, in the previous example, W50 = 50/100, W251 = 25/100, W252 = 25/100
Degree of polymerization & molecular weight
Suppose we want to find out the average population of each 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 average.
We learn about these differences, because different measurement techniques
measure different averages, and the ratio of Mw to Mn, called the Poly
Dispersity Index (PDI) often determines properties.
* taken from Polymer Physics by M. Rubinstein & R. H. Colby, 1st edition, OUP
 Polymer Architecture
Polymer = many mers
mer mer mer
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH 3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)

Covalent chain configurations and strength:

Direction of increasing strength

 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

C C C C C
Isotactic 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

C C C C C
Syndiotactic 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 C C Cant Crystallize

R H H R R H R H R H

Stereoisomerism
Polymer Architecture - Schematics
If you have some red
beads and some black
Random beads, how can you
make polymers out of
them ?

Alternating

Blocky

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 plastics

cross-linking
 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 Properties
Molecular weight Mw: Mass of a mole of chains.

smaller Mw 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 order

Amorphous disordered polymer chains in

the intercrystalline region

~10 nm spacing
Mechanical Properties of Polymers
 Elasticity of Polymers
Random arrangement = High Entropy Stretched = Low Entropy

Entropy is a measure of randomness: The more ordered the chains are, the lower
is the entropy. Spontaneous processes always tend to increase the entropy, which
means that after stretching, the chains will tend to return to a high-entropy state
 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

Thermoplastic (uncrosslinked) medium times Rubber-like Elastic

Deformation
Glassy (Elastic-high modulus)
Modulus of elasticity

Leathery
(Elastic-low modulus)

Rubbery Plateau
Elastic at high strain rate Long times Slow
Viscous at low strain rate relaxation

Tg Tm
Temp.
 Viscoelasticity: Structure Dependence
Effect of crosslinking Effect of crystallinity
Thermoset
Log Mod. Of Elasticity

Log Mod. Of Elasticity

Heavy Crosslinking
Elastomer 100 % crystalline
Light crosslinking

Branched polymer
50 % Crystalline
Thermoplastic amorphous
No crosslinking
Tg Tm
Tg Tm

Crystals act like crosslinks

Crosslinked Branched Strain Induced Crystallization in NR
 TENSILE RESPONSE: ELASTOMER
(ex: rubberband)

Compare to responses of other polymers:

--brittle response (aligned, cross linked & networked case)
--plastic response (semi-crystalline 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.
 TIME-DEPENDENT DEFORMATION
Stress relaxation test:
Data: Large drop in Er
(amorphous
--strain to o and hold. for T > Tpolystyrene)
g.
--observe decrease in
stress with time.

Relaxation modulus:

(t )
Er (t )
o
 Time-Temperature Superposition
Lo T
Log Relaxation Modulus

Relaxation Modulus

Hi T

Log Time
 Relaxation Modulus

Stress,
Glass-like elasticity
Rubber-like
elasticity

10 Fluid-like
Viscous
L 10 s time

Viscoelstic modulus
(10)
Modulus of elasticity E r (10s) =
L fixed
fixed Relaxation Modulus
Lo

Er(0)= E, Youngs Modulus

Er( )= 0