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Types of Stresses
F
Tensile
F
Compressive
Bending
F
F
Shear
Stress vs Strain
force
area
length
strain
length
stress
Units:
E: [GPa] or [psi]
: dimensionless
Plastic deformation
Irreversible:
Stress removed material does not return to
original dimensions.
Yield Strength ( y)
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
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
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
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
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
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.
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
Polypropylene (PP)
Linear
Branched
Cross-Linked
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.
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
some
red beads and
some black beads,
how can you make
polymers out of
them ?
Rando
m
Block
y
Alternati
ng
Branched
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
Elasticity of Polymers
Random arrangement = High Entropy
Viscosity of Polymers
Low entropy state
Elastic Deformation
creep
Slow Deformation
random
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
Tg
Temp.
Tm
Slow
relaxation
Heavy Crosslinking
Elastomer
Light crosslinking
Branched polymer
Thermoplastic
No crosslinking
Tg
Crosslinked
Tm
Viscoelasticity: Structure
Effect of crosslinking
Effect of crystallinity
Dependence
Thermoset
100 % crystalline
50 % Crystalline
amorphous
Tg
Branched
Tm
40
20
0
0
initial: amorphous chains are
kinked, heavily cross-linked.
elastomer
final: chains
are straight,
still
cross-linked
Deformation
is reversible!
Decreasing T...
--increases E
--increases TS
--decreases %EL
Increasing
strain rate...
--same effects
as decreasing T.
(MPa)
80 4C
60
40
20C
40C
20
0
0
60C
0.1
0.2
to 1.3
0.3
TIME-DEPENDENT DEFORMATION
Stress relaxation 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)
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
L
Lo
RelaxationModulus
(10)
fixed