ME 501: Microstructure and

Mechanical Properties
Fall 2020
Prof. Mustafa GÜDEN

Module-8
Structure and mechanical properties of polymers

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POLMERS-NATURAL VS SYNTHETIC
• Naturally occurring polymers used for many centuries; wood, rubber, cotton,
wool, leather, and silk.
• Biology: proteins, enzymes, starches, and cellulose found in plants and animals.
• Synthetic polymers: plastics, rubbers, and fiber materials.
• Synthetics polymers:
• inexpensive,
• properties can be altered
• The properties of polymers are intricately related to the microstructure

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HYDROCARBON MOLECULES
• Many organic materials are hydrocarbons;
hydrogen and carbon.
• The intramolecular bonds are covalent.
• Each carbon atom has four electrons that may
participate in covalent bonding, whereas every
hydrogen atom has only one bonding electron.
• Ethylene (C2H4) , the two carbon atoms are doubly
bonded together, and each is also singly bonded to
two hydrogen atoms;
• In Acetylene (C2H2) triple bond is found

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HYDROCARBON MOLECULES
• unsaturated hydrocarbon : each carbon atom is not bonded to the maximum (or
four) other atoms
• saturated hydrocarbon, all bonds are single ones, and no new atoms may be
joined without the removal of others that are already bonded.
• paraffin family: the chainlike paraffin molecules include methane (CH4), ethane
(C2H6), propane (C3H8), and butane (C4H10). The covalent bonds in each
molecule are strong, but only weak hydrogen and van der Waals bonds exist
between molecules,
• These hydrocarbons have relatively low melting and boiling points. Boiling
temperatures rise with increasing molecular weight.

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HYDROCARBON MOLECULES

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HYDROCARBON MOLECULES
• Isomerism: Hydrocarbon compounds with the same composition but in different
atomic arrangements.

normal butane

Tb=0.5oC isobutane
Tb=12.3 oC

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HYDROCARBON MOLECULES
• R and R’ represent organic
radicals—groups of atoms that
remain as a single unit and
maintain their identity during
chemical reactions.
• Examples of singly bonded
hydrocarbon radicals include the
CH3, C2H5 , and C6H5 (methyl,
ethyl, and phenyl) groups.

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POLYMER MOLECULES
• The gigantic molecules in polymers: macromolecules.
• Covalent interatomic bonds in in the form of long and flexible chains, the back
bone: a string of carbon atoms;
• Long molecules: structural mer units,
• ‘‘Mer’’ originates from meros (part), and the term poly (many)
• Polymer means many mers.

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CHEMISTRY OF POLYMER MOLECULES
Hydrocarbon ethylene (C2H4) (a gas at ambient
temperature and pressure) .

An active mer is formed by the reaction between

an initiator or catalyst species (R.) and the
ethylene mer unit .

The polymer chain forms by the sequential

addition of polyethylene monomer units to this
active initiator-mer center.

The final result is the polyethylene molecule.

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CHEMISTRY OF POLYMER MOLECULES
The angle between the singly bonded carbon atoms is close to 109o .
The carbon atoms form a zigzag pattern, the C__ C bond length being 0.154 nm.

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CHEMISTRY OF POLYMER MOLECULES
• If all the hydrogen atoms in polyethylene are replaced by
fluorine, the resulting polymer is poly-tetra-fluoro-ethylene
(PTFE or teflon).
• PTFE belongs to a family of polymers called the
fluorocarbons.
• Homopolymer: all the repeating units along a chain are the
same type.
• Copolymers composed of two or more different mer units,

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MOLECULAR WEIGHT
• Molecular weight, Mw: Mass of a mole of chains.

The number average molecular weight Mn A weight-average molecular weight Mw

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MOLECULAR WEIGHT
• Both number-average (𝑛𝑛 ) and weight-average (𝑛𝑤 ) degrees of polymerization
(DP) are possible, as follows:

• while m is the mer molecular weight. For a copolymer (having two or more
different mer units), m is determined from

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MOLECULAR WEIGHT
• The number-average molecular weight of a polypropylene is 1,000,000 g/mol.
Compute the number-average degree of polymerization.

m = 3(AC) + 6(AH) = (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol

𝑀𝑤 106 g/mol
𝑛𝑛 = = = 23,700
𝑚 42.08 g/mol

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MOLECULAR WEIGHT
• Melting temperature is raised with increasing molecular weight (for M up to
about 100,000 g/mol).
• At room temperature, polymers with very short chains (having molecular weights
on the order of 100 g/mol) exist as liquids or gases.
• Those with molecular weights of approximately 1000 g/mol are waxy solids (such
as paraffin wax) and soft resins.
• Solid polymers (sometimes termed high polymers), which are of prime interest
here, commonly have molecular weights ranging between 10,000 and several
million g/mol.

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MOLECULAR SHAPE
• Single chain bonds: rotation and bending in three dimensions.
• A straight chain segment results when successive chain atoms are positioned.
• On the other hand, chain bending and twisting are possible when there is a
rotation of the chain atoms into other positions.

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MOLECULAR STRUCTURE
• LINEAR POLYMERS: mer units joined together end to end in single
chains. (Thermoplastics). There may be extensive van der Waals
and hydrogen bonding between the chains. polyethylene, polyvinyl
chloride, polystyrene, polymethyl methacrylate,nylon, and the
fluorocarbons.
• BRANCHED POLYMERS with side-branch. The chain packing
efficiency is reduced with the formation of side branches, which
results in a lowering of the polymer density. Those polymers that
form linear structures may also be branched.
• CROSSLINKED POLYMERS linear chains are joined one to another
at various positions by covalent bonds. Often, this crosslinking is
accomplished (during synthesis by a chemical reaction) by additive
atoms or molecules that are covalently bonded to the chains. Many
of the rubber elastic materials are crosslinked; called Vulcanization.
• NETWORK POLYMERS mer units having three active covalent
bonds, a polymer that is highly crosslinked may be also classified as
a network polymer. The epoxies, polyester and phenol-
formaldehyde belong to this group.
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THERMOPLASTIC AND THERMOSETTING POLYMERS
• Thermoplastics
• soften when heated and eventually liquefy
• harden when cooled
• as the temperature is raised, the relative movement of adjacent chains is facilitated (little cross
linking)
• relatively soft and/or ductile.
• Most linear polymers and those having some branched structures with flexible chains are
thermoplastic.
• These materials are normally fabricated by the simultaneous application of heat and pressure.
• Thermosets
• become permanently hard when heat is applied and do not soften upon subsequent heating.
• Large cross linking (10 to 50% of the chain mer)
• Only heating to excessive temperatures will cause severance of these crosslink bonds and polymer
degradation.
• harder and stronger than thermoplastics, and have better dimensional stability.
• vulcanized rubbers, epoxies, and phenolic and some polyester resins

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COPOLYMERS
• random copolymer two different units are randomly
dispersed along the chain
• alternating copolymer the two mer units alternate
chain positions
• block copolymer: identical mers are clustered in
blocks along the chain
• graft copolymer homopolymer side branches of one
type may be grafted to homopolymer main chains
that are composed of a different mer;

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POLYMER CRYSTALLINITY
• polymer crystallinity: packing of molecular
chains so as to produce an ordered atomic
array.
• polymer molecules: partially crystalline (or
semicrystalline), having crystalline regions
dispersed within the remaining amorphous
material.
• Twisting, kinking, and coiling of the chains
prevent the ordering. crystalline
region

amorphous
region

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POLYMER CRYSTALLINITY
• The degree of crystallinity by weight may be determined from density measurements,

• where rs is the density of a specimen, ra is the density of the totally amorphous polymer, and
rc is the density of the perfectly crystalline polymer.
• The density of a crystalline polymer will be greater than an amorphous one of the same
material and molecular weight, since the chains are more closely packed together for the
crystalline structure.
• Crystallization is difficult in chemically complex structures.
• Linear polymers: crystallization is easy, no restrictions to prevent chain alignment.
• Excessive branching prevents crystallization
• Most network and crosslinked polymers almost totally amorphous;
• Alternating and block copolymers there is some likelihood of crystallization. The random and
graft copolymers are normally amorphous.
• Crystalline polymers are usually stronger and more resistant to dissolution and softening by
heat.
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SUMMARY
• Polymers are very large molecules—chains of carbon atoms, to which are side-bonded various atoms or
radicals.
• Composed of mers, repeating along the chain.
• A distribution of molecular weights expressed in terms of number and weight averages.
• Chain length specified by degree of polymerization, the number of mer units per average molecule.
• Molecular entanglements occur twisted, coiled, and kinked shapes
• With regard to molecular structure, linear, branched, cross-linked, and network structures are possible,
• The copolymers include random, alternating, block, and graft types.
• Thermoplastic: linear and branched structures; they soften when heated and harden when cooled.
• Thermosets not soften upon heating; their structures are cross-linked and network.
• Polymers may also exhibit varying degrees of crystallinity; crystalline regions are interdispersed within
amorphous areas.
• Crystallinity is facilitated for polymers that are chemically simple and that have regular and symmetrical
chain structures.

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Mechanical behavior of polymers
• All polymers have a spectrum of mechanical behavior, from brittle-elastic at low
temperatures, through plastic to viscoelastic or leathery, to rubbery and finally
to viscous at high temperatures.
• Between −20 C and 200 C a polymer can pass through all of the mechanical
states, and in doing so its modulus and strength can change by a factor of 103 or
more.
• While metals and ceramics are treated as having a constant stiffness and strength
for design near ambient temperatures, polymers cannot be treated so.
• The mechanical state of a polymer depends on its molecular weight and on the
temperature; or, more precisely, on how close the temperature is to its glass
temperature Tg. Each mechanical state covers a certain range of normalized
temperature T/Tg.

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Mechanical behavior of polymers
Linear polymer

1000

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Mechanical behavior of polymers
• Some polymers, like PMMA, and many epoxies, are brittle at room temperature
because their glass temperatures are high and room temperature is only 0.75 Tg.
• Polyethylenes, are leathery; for these, room temperature is about 1.0 Tg.
• Still others, like polyisoprene, are elastomers; for these, room temperature is
well above Tg (roughly 1.5 Tg).
• So it makes sense to plot polymer properties not against temperature T , but
against T/Tg since that is what really determines the mechanical state.

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Mechanical behavior of polymers

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Mechanical behavior of polymers

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Elastic modulus
(a) the glassy regime, with a large modulus, around 3 GPa;
(b) the glass-transition regime, in which the modulus drops steeply from 3 GPa to
around 3 MPa;
(c) the rubbery regime, with a low modulus, around 3 MPa;
(d) the viscous regime, when the polymer starts to flow;
(e) the regime of decomposition in which chemical breakdown starts.

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The glassy regime
• The glass temperature is the temperature at which the secondary bonds start to
melt.
• Well below Tg the polymer molecules pack tightly together. Load stretches the
bonds, giving elastic deformation which is recovered on unloading.
• There are two sorts of bonds: the strong covalent bonds that form the backbone
of the chains; and the soft secondary bonds between them.
• The modulus of the polymer is an average of the stiffnesses of these two bonds.

cross-linked f = 1 then the modulus

f is the fraction of stiff, covalent bonds
(modulus E1) and (1 – f) is the fraction of
weak, secondary bonds (modulus E2).
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E1=1000 GPa (daimond) is
known:, then the modulus E2 is that
of a simple hydrocarbon like paraffin
wax, and that is known: it is 1 GPa.
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The glassy regime

A schematic of a linear-amorphous polymer, showing the strong covalent bonds (full lines) and the weak secondary bonds
(dotted lines). When the polymer is loaded below Tg, it is the secondary bonds which stretch.
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The glassy regime This orientation strengthening is a potent way of increasing the
modulus of polymers. The stiffness normal to the drawing
direction, of course, decreases because f falls towards zero in
that direction.

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The glassy regime
• Glassy modulus (which, like that of metals and ceramics, is just due to bond-
stretching) should not depend much on temperature.
• But the tangled packing of polymer molecules leaves some "loose sites" in the
structure: side groups or chain segments, with a little help from thermal energy,
readjust their positions to give a little extra strain.
• These secondary relaxations can lower the modulus by a factor of 2 or more, so
they cannot be ignored.

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The glass, or visco-elastic transition
As the temperature is raised, the secondary bonds start to
melt. Then segments of the chains can slip relative to each
other like bits of greasy string, and the modulus falls steeply.

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The glass, or visco-elastic transition
• When the polymer is loaded, bits of the molecules slide slightly in the tubes in a
snake-like way (called “reptation”) giving extra strain and dissipating energy.
• As the temperature rises past Tg, the polymer expands and the extra free volume
lowers the packing density, allowing more regions to slide, and giving a lower
apparent modulus.
• But there are still nonsliding (i.e. elastic) parts. On unloading, these elastic
regions pull the polymer back to its original shape, though they must do so
against the reverse viscous sliding of the molecules, and that takes time.
• The result is that the polymer has leathery properties, as do low-density
polyethylene and plasticised PVC at room temperature.

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The glass, or visco-elastic transition
Same modulus

where C1 and C2 are constants.

This is called the “WLF equation”
after its discoverers, Williams,
Landel and Ferry, and (like the
Arrhenius law for crystals) is
widely used to predict the effect
of temperature on polymer
behaviour. If To is taken to be the
glass temperature, then C1 and
C2 are roughly constant for
all amorphous polymers (and
inorganic glasses too); their
values are C1 = 17.5
and C2 = 52 K.

Above Tg

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Rubbery behaviour and elastomers
• As the temperature is raised above Tg,
flow in the polymer become easier and
easier, until it becomes a rather sticky
liquid.
• Linear polymers with fairly short chains
(DP < 103 ) do just this.
• But polymers with longer chains (DP >
104 ) pass through a rubbery state

A schematic of a linear-amorphous polymer, showing entanglement points

(marked "E") which act like chemical cross-links.
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Rubbery behaviour and elastomers
• The long molecules form entanglements and because of their length and
flexibility, become knotted together.
• On loading, the molecules reptate (slide) except at entanglement points.
• The entanglements give the material a shape-memory: load it, and the segments
between entanglements straighten out; remove the load and the wriggling of the
molecules (being above Tg) draws them back to their original configuration, and
thus shape.
• Stress tends to order the molecules of the material; removal of stress allows it to
disorder again.
• The rubbery modulus is small, about one-thousandth of the glassy modulus and
gives the plateau in the modulus.

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Rubbery behavior and elastomers
• The number of cross-links must be small—about 1 in every few hundred
monomer units. The covalent cross-links do not melt, and this makes the polymer
above Tg into a true elastomer, capable of elastic extensions of 300% or more
which are recovered completely on unloading.
• Over-frequent cross-links destroy the rubbery behavior. If every unit on the
polymer chain has one (or more) cross-links to other chains, then the covalent
bonds form a three-dimensional network, and melting of the secondary bonds
does not leave long molecular spans which can straighten out under stress.
• Good elastomers, like polyisoprene (natural rubber) are linear polymers with just
a few cross-links, well above their glass temperatures (room temperature is 1.4 Tg
for polyisoprene). If they are cooled below Tg, the modulus rises steeply and the
rubber becomes hard and brittle, with properties like those of PMMA at room
temperature.
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Viscous flow
• At higher temperatures (>1.4 Tg) the secondary bonds melt completely and even the
entanglement points slip.
• This is the regime in which thermoplastics are molded; linear polymers become viscous
liquids. The viscosity is usually measured in shear:

(Poise or 10-1 Pa.s)

• Polymers, like inorganic glasses, are formed at a viscosity in the range 104 to 106 poise,
when they can be blown or molded.
• When a metal melts, its viscosity drops discontinuously to a value near 10−3 poise—
about the same as that of water; that is why metals are formed by casting, not by the
more convenient methods of blowing or molding.)
• Cross-linked polymers do not melt. But if they are made hot enough, they, like linear
polymers, decompose.
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Viscous flow
• In the temperature range 1.3–1.5 TG, where most thermoplastics are formed, the
flow has the same time–temperature equivalence as that of the viscoelastic
regime

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Decomposition
• If a polymer gets too hot, the thermal energy exceeds the cohesive energy of
some part of the molecular chain, causing depolymerisation or degradation.
• Some (like PMMA) decompose into monomer units; others (PE, for instance)
randomly degrade into many products.
• It is commercially important that no decomposition takes place during high-
temperature moulding, so a maximum safe working temperature is specified for
each polymer; typically, it is about 1.5 Tg.

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Modulus diagrams for polymers

A modulus diagram for

PMMA. It shows the glassy
regime, the glass-rubber
transition, the rubbery regime
and the regime of viscous
flow. The diagram is typical of
linear-amorphous polymers.

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Effect of cross-linking

Cross-linking raises and extends

the rubbery plateau, increases
the rubber-modulus, and
suppresses melting.

Crystallisation increases the

modulus, do not suppress
melting, so crystalline linear-
polymers (like high-density PE)
can be formed by heating and
molding them, just like linear-
amorphous polymers; cross-linked
polymers cannot.
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Strength
(a) brittle fracture, like that in ordinary glass;
(b) cold drawing, the drawing-out of the molecules in the solid state, giving a large
shape change; '
(c) shear banding, giving slip bands rather like those in a metal crystal;
(d) crazing, a kind of micro-cracking, associated with local cold-drawing;
(e) viscous flow, when the secondary bonds in the polymer have melted.
Brittle fracture
• Below about 0.75 Tg, polymers are brittle.
• A polymer sample has small surface cracks
(depth c) left by machining or abrasion, or
caused by environmental attack.
• Then a tensile stress a will cause brittle failure
if

• The fracture toughness of most polymers is 1

MPa m1/2 and the incipient crack size is,
typically, a few microns. Then the fracture
strength in the brittle regime is about 100 MPa.

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Cold drawing
• At temperatures 50°C or so below Tg,
thermoplastics become plastic. The
stress-strain curve typical of polyethylene
or nylon shows three regions.
• At low strains the polymer is linear
elastic,
• At a strain of about 0.1 the polymer
yields and then draws. The neck
propagates along the sample until it is all
drawn. The drawn material is stronger in
the draw direction.
• When drawing is complete, the stress-
strain curve rises steeply to final fracture.
This draw-strengthening is widely used to
produce high-strength fibers and film.

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Crazing
• Many polymers, among them PE, PP and nylon,
draw at room temperature. Others with a higher
Tg, such as PS, do not—although they draw well
at higher temperatures.
• If PS is loaded in tension at room temperature it
crazes. Small crack-shaped regions within the
polymer draw down, but being constrained by
the surrounding undeformed solid, the drawn
material ends up as ligaments which link the
craze surfaces.
• Crazes are easily visible as white streaks or as
general whitening.
• They are a precursor to fracture. Before drawing
becomes general, a crack forms at the centre of a
craze and propagates—often with a crazed zone
at its tip—to give final fracture

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Shear banding
• When crazing limits the ductility in
tension, large plastic strains may still
be possible in compression shear
banding.
• Within each band a finite shear has
taken place. As the number of bands
increases, the total overall strain
accumulates.

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viscous flow
• When the secondary bonds in the polymer have melted strength falls greatly
Strength diagram

A strength diagram for PMMA. The diagram is, as far as is known, broadly typical of linear polymer
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Predicting stress strain curves
• PC

Tg= 147 °C

T/Tg=(298/(140+273)=0.73
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Predicting stress strain curves

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