POLYMERIC MATERIALS (POLYMERS)

General Structure
The name polymer gives an indication of the structure of these materials. Poly means many and
mer means units. Polymeric structures are either long chains of repeating molecules (called
macromolecules) or large networks of repeating molecules. Usually the chain or network has a
carbon backbone with hydrogen and other elements arranged on it such as ! "! #! $i! $. %ence
most polymers are organic materials. There are also inorganic polymers that we will not discuss here.
&ovalent bonds act between the molecules on the chains or networks (intra'molecular forces)(
secondary bonds act between the chains and in the networks (inter'molecular forces).
Polymers can be anywhere from ) ' *)+ crystalline. ,f they do crystalli-e! the structures tend to be
very comple.. ,n general crystallinity will affect the properties by increasing the packing and hence
the secondary bonding forces! making the material stronger and more rigid! and hence! less ductile.
General Properties
/ightweight
/ow strength
,nsulative
0uctile
1ood noise and vibrational dampers
Three Main Classifications of Polyeric Materials
2. Theroplastic Polyers or Theroplasts
!
These materials soften when heated and eventually li3uefy. They harden when cooled. These
processes are reversible so that they can be reheated and reformed. %ence they are recyclable.
They are usually soft and ductile and can be easily fabricated by heat and pressure.
They usually have a linear structure with fle.ible chains and come from chain polymeri-ation.
4.amples include polyethylene! polyvinyl chloride (P5&)! polypropylene (PP)! Polystyrene
&ommon possessing techni3ues include in6ection molding and e.trusion molding.
7. Therosettin" Polyers or Therosets
These materials become permanently bonded or set by chemical reactions that take place when
heated or provided with a catalyst. %ence they become more rigid when heated. %owever! they do
not soften when the temperature is returned to ambient because these reactions are irreversible. ($o
they are not recyclable. ' This is opposite to thermoplastic behavior which become softer when heated
and then harder when the temperature returns to ambient because the process is reversible.)
Thermosets usually do not li3uefy at higher temperatures! but instead char. They are usually harder!
stronger! more brittle! more dimensionally stable! and more resistant to heat and creep than
thermoplastics.
They usually have a rigid cross'linked or network structure from condensation polymeri-ation.
4.amples include vulcani-ed rubber! epo.ies! phenolic resins! polyester resins.
They are not easily processed. &ommon processing techni3ues include compression molding and
transfer molding.
8. Elastoers
These can be elastically deformed a very large amount. (799 ' 2999+) There are both thermoplastic
elastomers and thermosetting elastomers.
1 The word plastic is used in many different ways and so can be very confusing.
$ometimes it is used as a synonym for the word polymer although this is not strictly correct.
$ometimes it is used as a synonym for thermoplastic polymers which is 6ust one of the three classifications of polymers.
$ometimes it is used to mean a polymer that has elastic! yielding and plastic regions in the s'e curves! similar to metals.
$ometimes it is used to mean the largest category of polymer applications.
Alternati#e Classification of Polyeric Materials
2. En"ineerin" Polyers
:ny polymer with sufficient strength and stiffness to be serious candidates for structural applications
once dominated by metals.
7. General purpose polyers
,ncludes various films! fabrics and packaging materials.
$% Elastoers
:s always! these are imperfect categori-ations and there is overlap.
Polyeri&ation Reactions
Polymers are made or polymeri-ed by chemical reactions. These reactions bond small simple hydrocarbon
(organic) molecules from coal and petroleum products! usually in the gaseous state! into large
macromolecules (long chains or networks) that are solids. There are two types of polymeri-ation reactions.
!% A''ition (Chain Gro(th) Polyeri&ation
involves a rapid chain reaction of chemically activated mers
each reaction sets up the condition for another to proceed
each step needs a reactive site (a double carbon bond or an unsaturated molecule)
the three stages are; initiation! propa"ation! terination
(,n the case of the polymeri-ation of polyethylene! initiation can come from a free ra'ical <
a single unit that has one unpaired electron such as an %=

molecule. %77 can break up
into 7 %=

molecules. 4ach can act to initiate and to terminate the reaction. The
termination here would be called reco)ination.)
the composition of resultant molecule is a multiple of the individual mers
these reactions most commonly produce linear structures but can produce network
structures
*% Con'ensation (Step Gro(th or Step(ise) Polyeri&ation
individual chemical reactions between reactive mers that occur one step at a time
slower than addition polymeri-ation
need reactive functional groups
a byproduct such as water or carbon! o.ygen or hydrogen gas is formed
no reactant species has the chemical formula of a mer repeat unit
most commonly produces network structures but can produce linear structures
Soe of the coon siple hy'rocar)ons that "o into the polyeri&ation reactions+

4thylene ' &7%> note the ?ene@ ending indicates an unsaturated molecule

:cetylene ' &7%7 i.e. a molecule with one or more double or triple bonds

Aethane ' &%>

4thane ' &7%B

Cutane ' &>%29 This is the paraffin family &n%7nD7

Pentane ' &)%27 note the ?ane@ ending indicates a saturated molecule

%e.ane ' &B%2> i.e. a molecule with only single bonds

&arbon has four electrons in sp
8
orbitals that can each form a covalent bond. ,f each of these electrons bond
with a different atom! the bonds will all be single bonds. ,f two (or three) of these electrons bond with the
same atom! then there will be a double (or triple) bond.
Soe coon polyers that result fro these polyeri&ation reactions+
Polyethylene (P4)
Polytetrafluoroethylene (PT#4) aka Teflon ' a member of the fluorocarbons
Polyvinyl &hloride (P5&)
Polypropylene (PP)
Polystyrene (P$) vinyl polymers or vinyls (one % on each mer is replaced)
Polyacrylonitrile
Polyvinylacetate
Polymethylmethacrylate (PAA:) vinylidene polymers or vinylidenes
Polyvinylidene chloride (two % atoms on each mer are replaced)
As MW
so does Tm
Si&e of Polyeric Molecules
Aolecular si-e is 3uantified by the 'e"ree of polyeri&ation, -P (the number of mers on a molecular chain)
or as its olecular (ei"ht.
$ince there are varying si-es of molecules! a statistical distribution must be used to 3uantify it.
The four methods are;
2. weight average degree of polymeri-ation! nn
7. number average degree of polymeri-ation! nw :s n or A increases!
8. weight average molecular weight! Aw temperature so does melting point
>. number average molecular weight! An and solidness. (EhyF)
The molecular length is obtained by considering the fact that the bond angle for the sp
8
hybrid orbitals of
&arbon is 29*
o
. This gives the chain a -ig'-ag configuration. The e.tended length of the molecule can be
calculated as; /e.t G ml Hsin (29*
o
I7)J where l is the length of a single bonds in the backbone of hydrocarbon
chain and m is the number of bonds. (note mG7n)
%owever! there is more to the story as you consider that a single bond along the chain can rotate 8B9
o
to give
a very kinked! coiled and twisted conformation. The effective length of the molecule! from a statistical
analysis of a freely kinked linear chain! is therefore / G l m called the root mean s3uare length.
Polyer Molecular Structure
Linear or chain structures are formed from )ifunctional mers. These can have side groups attached.
o Isotactic
side group mers are all on the same side
o Syn'iotactic
side group mers alternate on different
sides of the chain
o Atactic
side group mers are positioned randomly
on one side or the other
o .oopolyers
The chain has the same mers along the entire length. :nalogous to a pure metal.
o Copolyers
The mers are different along the length of the chain. :nalogous to a metallic solid solution.
There are four types of copolymers;
Kandom
:lternating
Clock
1raft
o /len's
0ifferent types of polymeric molecules are mi.ed together. (:nalogous to metallic alloys with limited
solid solubility.)
/ranche' structures
are structures where a
chain is attached to a
point on another linear chain.
Crosslin0e' structures are structures where chains
are connected at various points. #or e.ample an
important process in elastomers is called #ulcani&ation
which is essentially 6ust crosslinking. ,t is a nonreversible
chemical reaction at high temperature in which $ulfur
atoms bond with ad6acent polymer backbones. /ight
crosslinking that is widely dispersed throughout material
gives the best properties. ($ilicone rubbers replace the
'&' with '$i<' on the backbone)
1et(or0 structures are formed from trifunctional or polyfunctional mers.
1ote that in "eneral ri"i'ity an' eltin" point ten' to rise (ith+
o higher AE
o more side groups
o more branching
o crosslinking
o more networked structures
This effect is due to hindrances to molecular sliding and greater secondary bonding forces acting.
Polyer Crystallinity
The polymer structures tend to be very comple. because they involve large molecules. ,n fact the unit cell
might only include a portion of a molecular chain. 0ue to the comple.ity of the structure! the chain disorder!
misalignment! etc. )'*)+ of the volume of a polymer can be non'crystalline.
$emi'crystalline structures can be compared to two'phase metals. The percent crystallinity can be found by
measuring the density and knowing the density of the crystal phase and the amorphous phase;

The degree of crystallinity will increase with;
$lower cooling rates
$implicity of chain structure note; the more randomness
$implicity of mer chemistry and irregularity!
/ess side branching the less crystallinity
&hain regularity (isotactic or syndiotactic)
:s crystallinity increases so does;
0ensity
$trength
%eat resistance
&reep resistance
Polyer Crystal Mo'els
#ringed'Aicelle model
4arliest
$mall crystal regions embedded in an amorphous matri.
: single molecule could be in both regions
&hain'folded model
Kegular shaped thin platelets (lamellae) in a layered structure
&hains fold back and forth in the lamellae
$pherulites
4ach spherulite is made of an aggregate of ribbon'like chain folded crystallites (lamellea) that
radiate out from the center and are separated by amorphous regions that are linked by tie
molecules. They grow spherical in shape until they hit each other and become like a Aaltese
#alcon design.
4.amples of polymers with this structure are P4! PP! P5& L PT#4
Meltin" Teperature

2 Glass Transition Teperature of Polyers
Tm L Tg usually define! respectively! the upper and lower temperature limits for applications of semi'crystalline
polymers. Tg may also define the upper use temperature for amorphous materials.
Metho's use' to increase T 2 T"+
!% Increase M3
Aelting can take place over a range of temperatures due to the variation of AE
*% Increase secon'ary )on'in"
polar side groups! crystallinity! ether or amide linkages on the main chain
$% -ecrease chain fle4i)ility5increase chain stiffness
double bonds! aromatic groups! bulky and large side groups
6% Increase crosslin0in"
7% Increase 'ensity of )ranchin"
: small amount of branching may lower Tm L Tg because it will decrease crystallinity.
8% Increase the thic0ness of the laellae
&rystalli-ing the solid at a low temperature or annealing 6ust below Tm will do this.
9% Increase the rate of heatin"
Specific "lassy ri"i' supercoole' li:ui' li:ui'
;olue )rittle soli' leathery ru))ery (viscous
(elastic behavior) (visco'elastic behavior)
behavior)
non<
crystalline
sei<crystalline
crystalline regions in a
supercooled li3uid (or viscous
solid) matri..
crystalline < more efficient packing
causes sudden decrease in specific vol
T" T Teerature
The #iscosity, can specify the behavior of polymers in these various regions. The viscosity is the material
property that measures resistance to flow by shear forces. ,t is the proportionality constant between the
shear stresses and the velocity gradient; = dv/dy
;iscoelasticity is a combination of viscous and elastic behavior. ,t is both time dependent (a form of
anelasticity) and temperature dependent. (Think of silly putty.)
The phenomenon of #iscoelastic Creep a result of viscoelasticity.
,t is the time'dependent deformation of polymers when the stress level is maintained constant.
,t will depend on temperature and can even have significant effects at room temperature for polymeric
materials. &reep tests are conducted in same manner as for metals.
: common parameter to 3uantify this behavior of polymeric materials is the creep o'ulus, Ec(t) = o5(t)
where (t) is the measured time dependant strain and o is the constant stress level at a specific
temperature.
The phenomenon of stress rela4ation is also a result of viscoelasticity.
,t is the time'dependent rela.ation of stress when the strain level is maintained constant.
,t will depend on temperature and can even have significant effects at room temperature for polymeric
materials.
: common parameter to 3uantify this behavior of polymeric materials is the rela4ation o'ulus, Er = (t)5o
where (t) is the measured time dependant stress and o is the constant strain level at a specific temperature.
Mechanical Properties of Polyeric Materials
Tensile modulus (or 4lastic Aodulus or 6ust modulus) is the same as Moung@s Aodulus for metals
but the values tend to be much lower for polymers. #or semi'crystalline polymers the tensile
modulus can be considered to be a combination of the modulus of the crystalline regions and the
amorphous regions.
Tensile $trength! ,mpact $trength (,-od or &harpy ,mpact $trengths)! #atigue $trengths are
defined in the same way as for metals and also have values that tend to be much lower for
polymers.
0uctility values are usually much higher for polymers than metals.
#atigue curves are same as for metals. $ome polymers have fatigue limits! others do not. The
values tend to be lower than for metals and much more dependent on loading fre3uency.
Tear $trength is the energy re3uired to tear apart a cut specimen that has a standard geometry.
(Kelated to T$)
%ardness! like metals! measures the resistance to penetration! scratching! or marring the surface.
0urometer and Carcol are common %ardness tests for polymers.
Polyer properties are #ery sensiti#e to+
Temperature ( T T$ 4 and 0uctility)
$train rate (strain rate has the same effect as T)
4nvironment (moisture! o.ygen! U5 radiation! organic solvents)
Typical stress<strain cur#es for the three 'ifferent types of polyers+
/rittle Polyers
(fail while elastically deforming)
Plastic
Polyers
(like metals! they have elastic region! yielding!
and then plastic behavior)
Elastoers
(rubber'like elasticity; large
recoverable strains at low
stresses)

-eforation of Polyers
Polymers in general e.perience large elastic and plastic deformations. (%ence the term plastics.)
4lastic deformations in thermoplastics come from chains uncoiling and stretching. This is reversible. Ehen
forces are removed! the chains revert to their original conformations. n the atomic level the primary bonds
are being stretched but not broken.
Plastic deformations come from the chains moving past one another. n the atomic level the secondary
bonds are being broken and reformed. #inally! with enough stress! the primary covalent bonds within the
chains are broken.
:ny double bond on a chain is rotationally rigid and so will restrict ability of chain to rotate freely! making the
material more rigid.
Culky side groups will also restrict chain rotation (called steric hindrance) making the material more rigid.
The property of a polymer can vary greatly with T. &onsider the plot of modulus of elasticity as a function of
temperature for a typical thermoplastic with appro.imately )9+ crystallinity;
Celow Tg the polymer behaves like a metal or ceramic. (:lthough the
value of the modulus is substantially lower.)
,n the Tg range! the modulus drops precipitously and the mechanical
behavior is termed leathery < it can be e.tensively deformed and
slowly returns to original shape upon removal of the stress.
Nust above Tg a ru))ery plateau is observed. ,n this region
e.tensive deformation is possible with rapid spring back to the
original shape upon removal of the stress.
"otice that with polymers we have e.tensive nonlinear elastic
'eforation.
Ehen Tm is reached! the modulus again drops precipitously and we
enter the li3uid'like viscous region. (: more precise term would be
decomposition point rather than a melting point.)
The behavior of the )9+ crystalline thermoplastic is midway between the fully crystalline material and a fully
amorphous material.
: structural feature that will affect the mechanical behavior in polymers is cross<lin0in" of ad6acent linear molecules to
produce a more rigid! network structure. The effect is similar to increasing crystallinity.
50% amorphous/50% crystalline
(See previous fiure!
Elastoers
are materials that e.perience vast elastic deformations. The huge elastic strains in these materials are
primarily due to uncoiling of the long chained molecules. 0eformation is also due to the sliding of molecular
chains over each other (breaking and reforming secondary bonds) and then finally the stretching of primary
bonds along the backbone of the carbon chain. %ence the elastic modulus increases with increasing strain
as shown here in the stress < strain curve for a typical elastomer;
The low strain modulus has a low value because the forces
needed to uncoil the molecular chains are small. The high'
strain modulus has a higher value because stronger forces
are needed to stretch the primary (covalent) bonds. Coth
regions involve overcoming secondary bonding! which is why
the elastic modulus for these materials is significantly less
than for metals or ceramics.
Tabulated values for the elastic modulus for elastomers are
usually for the low strain regions.
"ote that the recoiling of the molecules (during unloading) has a slightly different path than the uncoiling
(during loading). This defines hysteresis. %ysteresis is behavior in which a material property plot follows a
closed loop. ,n other words! it does not retrace itself upon the reversal of an independent variable! in this
case the stress. The area of the loop is proportional to the energy absorbed in each cycle of the loading.
-eforation of Elastoers
4lastomeric deformations are very large and recoverable. The tensile modulus of elastomers is typically
small and varies with strain. (i.e. it is non'linear)
This behavior comes from the elastomeric structure;
2. %ighly amorphous with twisted! coiled and kinked chains. 0uring deformation! these partially
straighten. Upon release of stress! they return to their original conformations.
7. &hain bond rotations are free.
&ross'linking provides a mechanism to delay plastic deformation by acting as anchors (chains sliding past
one another)
Consi'er the plot of o'ulus of elasticity as a
function of teperature for a typical elastoer+
The rubbery plateau is pronounced and establishes the
normal room'temperature behavior. (Tg is below room temp.)
The plot of o'ulus of elasticity as a function
of teperature for soe coercial elastoers+
"ote; 0TU/ in these curves is the deflection temperature
under load! a parameter fre3uently associated with Tg . (,t
is defined as the temperature at which a standard test bar
deflects a specified distance under a load. ,t is used to
determine short'term heat resistance. ,t distinguishes
between materials that are able to sustain light loads at
high temperatures and those that lose their rigidity over a
narrow temperature range.)
-ra(in"
The polymer analogy to the strain hardening of metals is called drawing. : polymeric tensile specimen
develops a neck! like metals do! but the necking e.tends to the entire length and starts at yielding. ,n
the neck region molecular chains are oriented in the direction of stress and hence the material has
become stronger in that direction. ($teps 7 ' > above.)
The resulting properties are highly anisotropic. The Tensile Aodulus can increase by 8 times in the
direction of drawing but be 2I) the original value at >)
o
to drawing. The resulting T$ in the direction of
drawing can be 7') times the original T$ but in the direction perpendicular to drawing it can be
reduced by 2I8 < O.
,f drawing is done to an amorphous polymer! the temperature must 3uickly be brought to ambient
temperatures! otherwise the effects will be lost.
%eat treating an un'drawn polymer structure will TA! M$! 0uctility because it will change
crystallite si-e and perfection and the spherulite structure. ("ote that this is opposite to what
annealing does to a metal.) %owever! heat treating a drawn polymer structure will do the opposite.
>racture of Polyers
Elastoers usually have ductile failures but can be brittle below Tg.
Theroplastics can fail in either ductile or brittle mode.
Celow Tg thermoplastics tend to have elastic behavior and fail in the brittle mode.
:bove Tg thermoplastics tend to behave plastically or viscously (sometimes called visco'elastic behavior) and
fail in the ductile mode.
Therosets usually have brittle failures.
$train rate will also affect which mode plastics will fail in; high strain rate will cause brittle failure! low strain
rates will cause ductile failure.
Stren"thenin" Mechaniss for Polyeric Materials
To stren"then Theroplasts+
2. ,ncrease AE (%owever AE does not affect 4)
7. ,ncrease the secondary bonding forces
(polar side groups! crystallinity! polar atoms such as ! " L $ on main chain in the form of amide
or ether linkages)
8. 0ecrease chain fle.ibilityI,ncrease chain stiffness
(double bonds! aromatic groups! bulky and large side groups that all cause steric hindrance)
>. ,ncrease cross'linking
). ,ncrease the density of branching
(: small amount of branching may lower strength because it will decrease crystallinity but a lot will
increase the strength by reducing chain mobility.)
B. :dd glass fibers
P. 0rawing
Cut! as usual! there will be a corresponding decrease in the ductility.
To stren"then Therosets+
2. ,ncrease the network.
7. :dd glass fibers.
Polyer A''iti#es
#oreign substances to modify and enhance the properties of polymers
Reinforceents5 fillers
To add strength! stiffness! abrasion resistance! toughness! dimensional L thermal stability! reduce
cost. (4.amples are wood flour! sand! glass! clay! talc! L limestone.)
Plastici&ers
To increase fle.ibility! ductility and toughness. Eill also lower strength and stiffness.
Sta)li&ers5.eat Sta)li&ers
To prevent degradations from uv radiation! o.idation andIor heat.
Colorants
pigments or dyes! to give color! opacity and weatherability.
>lae Retar'ants
To reduce combustibility.
Lu)ricants
To aid flow and prevent adhesion to metal surfaces.
Polyer >orin" Techni:ues
&ompression L Transfer molding
,n6ection molding
4.trusion
Clow molding
&asting
Coon Polyeric Materials
General Purpose Theroplastics
Polyethylene (P4)
Polyvinyl &hloride! P5&
Polypropylene (PP)
Polystyrene (P$)
Polyester
"ylons
:crylics (Polymethylmethacrylate! PAA: a.k.a. /ucite or ple.iglass)
$tyrene'acrylonitrile ($:")
Polyacrylonitrile
En"ineerin" Theroplastics
Polyamides ("ylons)
:crylonitrile butadiene styrene (:C$)
Polycarbonates
#lorocarbons (PT#4! P&T#4 a.k.a. teflon)
Phenylene .ide'based Kesins
:cetals
Polysulfones
Polyphenylene $ulfide
Polymer :lloys
Thermalplastic Polyesters (P4T! P4T4)
4po.ies
Therosets
Phenolics
4po.y Kesins
Unsaturated Polyesters
:mino Kesins (Ureas L Aelamines)
Elastoers
"atural Kubber (Polyisoprene)
$ynthetic Kubbers
$tyrene Cutadiene Kubber
"itrile Kubber (:crylonitrile'butadiene rubber)
&hloroprene ("eoprene)
$ilicone Kubber (Polysilo.ane)
A'#ance' Polyers
Ultra high molecular weight polyethylene (U%AEP4)
/i3uid &rystal Polymer
Thermoplastic elastomers (TP4 or 6ust T4)