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Crystallinity & Synthetic

Of polymers

atomic arrangements of polymer will
be more complex
As a consequence of their size and
often complexity, polymer molecules
are often only partially crystalline (or
crystalline regions dispersed within
the remaining amorphous material.
Any chain disorder or misalignment
results in an amorphous region
twisting, kinking, and coiling of the
chains prevent the strict ordering of
every segment of every chain.

There are some polymers that are completely amorphous, but

most are a combination with the tangled and disordered
regions surrounding the crystalline areas
The degree of crystallinity from completely amorphous (as
liquid) to almost entirely (~95%) crystalline (as solid)
That is, they form mixtures of small crystals and amorphous
material and melt over a range of temperature instead of at a
single melting point
The density of a crystalline polymer will be greater than an
amorphous one of the same material and molecular weight
the chains are more closely packed together for the crystalline

Factors affect degree of crystallinity

the rate of cooling during solidication, MW as well as on the
chain conguration.
1) Cooling rate
During crystallization upon cooling through the melting
temperature, the chains, which are highly random and
entangled in the viscous liquid must assume an ordered
For this to occur, sufcient time must be allowed for the
chains to move and align themselves
Slow cooling provides time for greater amounts of
crystallization to occur. Fast rates, on the other hand, such as
rapid quenches, yield highly amorphous materials.

2) MW
Low molecular weight polymers (short chains) are generally
weaker in strength. Although they are crystalline, only weak
Van der Waals forces hold the lattice together. This allows the
crystalline layers to slip past one another causing a break in
the material.
High DP (amorphous) polymers, however, have greater
strength because the molecules become tangled between
3) Chain configuration
The crystalline material shows a high degree of order formed
by folding and stacking of the polymer chains.
The amorphous or glass-like structure shows no long range
order, and the chains are tangled

Crystallization is not favored in polymers that are composed

of chemically complex repeat units (e.g., polyisoprene).
For linear polymers, crystallization is easily accomplished
because there are few restrictions to prevent chain alignment.
Any side branches interfere with crystallization that
branched polymers never are highly crystalline;
in fact, excessive branching may prevent any crystallization
Most network and crosslinked polymers are almost totally
amorphous because the crosslinks prevent the polymer
chains from rearranging and aligning into a crystalline
A few crosslinked polymers are partially crystalline
the bulkier or larger the side-bonded groups of atoms, the less
tendency there is for crystallization.

If the monomers are large and irregular difficult for the to

arrange an ordered manner, resulting in a more amorphous
Likewise, smaller monomers, and monomers that have a very
regular structure will form more crystalline polymers.
For copolymers, as a general rule, the more irregular and
random the repeat unit arrangements, the greater is the
tendency for the development of noncrystallinity.
For alternating and block copolymers there is some likelihood
of crystallization.
On the other hand, random and graft copolymers are normally
To some extent, the physical properties of polymeric materials
are inuenced by the degree of crystallinity.
Crystalline polymers are usually stronger and more resistant
to dissolution and softening by heat

Stages in polymer synthesis:
1) Polymerisation synthesize macromolecules from small
2) additive materials modifie & enhance the properties
3) finishing pieces fashione & shape product

monomers are linked together to generate long chains

composed of repeat units

raw material: derived from coal, natural gas, petroleum
2 classifications according reaction mechanism: addition &
condensation polymer

1) Addition polymerization
Chain reaction polymerization through free radical polymerisation

unsaturated carbon (organic) molecules react to form a long

chain polymer molecule
Free radical/ unpaired electron highly reactive, tend to rip
electron from other
Free radical are created by the division of initiator into two
Stability of free radical varies depending on the properties of
monomer units are attached one by one to an active site to form a
linear macromolecules -Result in exact multiple of original
synthesis of polyethylene, polypropylene, PVC
3 stages: initiation, propagation & termination affect MW
Stages are controlled to ensure degree of polymerization of



Begins when an initiator decomposes into free radical in the

present of monomer.
The instability of C-C double bond in monomer makes them
susceptible to reaction with the unpaired electron in the radical
active centre(location of unpaired electron) is formed by
reaction between an initiator (catalyst) species & monomer unit


R active initiator; unpaired electron

* In free radical polymerisation the radical attacks one monomer,
and the electron migrates to another part. This newly radical
attack another monomer & the process repeat.

ii) Propagation

linear growth of polymer chain by sequential addition of monomer

unit to the active growing chain molecule

1000 repeat units in 10-2 -10-3 s

In theory, the propagation continue until the supply of monomers
However, most often the growth of the chain is stopped by the
termination reaction

iii) Termination
2 ways:
a) combination
active end of free electron from 2 growing propagation chain may
link together form 1 molecule

b) disproportionation
free radical strips a hydrogen atom from an active chain
A C-C double bond takes the place of the missing hydrogen

2) Condensation polimerization
Stepwise intermolecular chemical reaction that may involve more
than 1 monomer species
bifunctional monomers react to form a long chain polymer molecule
By product: small MW (water) that is eliminated (condensed)
t condensation > t addition polymerisation
Polysaccharides, protein, thermosetting polyester & phenolformaldehyde, nylons, polycarbonates
intermolecular reaction occurs everytime a repeat unit is formed

Polyesters form when the -OH
functional group of one
monomer reacts with the
-COOH functional group of
another monomer.
An ester link (-COO-) is formed
between monomers during the
H2O is eliminated in the
General reaction between a
dicarboxylic acid and a diol:

Additives substances introduce to enhance/modify
properties, thus more serviceable: plasticizers,
stabilizers, colorants, flame retardants, fillers

# to improve tensile & compressive strength, abrasive
resistance, toughness, dimensional, thermal stability etc
# inexpensive materials that replace some vol of more
expensive polymer reduce cost
# wood flour (sawdust), silica flour, sand, glass, clay etc


Improve flexibility, toughness; reduce hardness & stiffness

Plasticizers are usually selected to be nonvolatile materials and
have good compatibility with the desired polymer.
Small plasticizer molecules occupy positions between large polymer
chain, increase interchain distance with reduction intermolecular
Used in brittle materials (Tr): PVC
Lower Tg at Tr, polymer may be used with some pliability &
(Liquids having low vapor P & low MW) phtalate ester, adipate
Application: PVC, thin sheet, film, tubing, raincoats

- Additive to counteract deterioration in some polymers
under normal environment expose to light-UV &
# Oxidation
chemical interaction between oxygen with polymer;
Stabilizer consume oxygen before it reaches polymer &/
prevent the oxidation reaction that would further damage
# Prevent photochemical degradation C black

UV radiation
interact with & cause severe in covalent bond &
molecular chain
- Approaches to UV stabilization: add UV absorbent & add
material react with broken bond
1) Add UV absorbent material
- layer at surface as sunscreen
- to block out the radiation before penetrating into &
damage the polymer
2) Add materials that react with bond broken by radiation
before they participate in other reactions lead more

- give color to polymer
- added as dyes
- molecules dyes dissolve in
-added as pigment filler
materials that do
- not dissolve, remain
separate phase
- small size & refractive index
near the parent polymers

Flame retardants
- Most all pure polymer are
- used in textile & toys
- interfere the combustion
process by initiating
different combustion
reaction generate less
heat, reduce T slowing

Polymer processing
There are a number of methods for producing polymer shapes,
including molding, extrusion, and manufacture of lms and bers.
The techniques depend to a large extent on the nature of the polymer
The greatest variety of techniques are used to form the thermoplastics.
The polymer is heated to near or above the melting temperature so
that it becomes rubbery or liquid.then formed in a mold or die to
produce the required shape.

A hollow preform of a thermoplastic called a parison is introduced
into a die by gas pressure and expanded against the walls of the
This process is used to produce plastic bottles, containers,
automotive fuel tanks, and other hollow shapes.


This is the most widely used technique for processing thermoplastics.

Extrusion can serve two purposes: 1) it provides a way to form certain simple
shapes continuously, and 2) extrusion provides an excellent mixer for additives
(e.g., carbon black, llers, etc.)
A screw mechanism consisting of one or a pair of screws (twin screw) forces
heated thermoplastic (either solid or liquid) and additives through a die opening
to produce solid shapes, lms, sheets, tubes, pipes, and even plastic bags.
The extruder consist of dierent heating or cooling zones. Extrusion can be
used to make film, coat wires and cables with either thermoplastics or

Thermoplastics heated above the melting temperature using an
extruder are forced into a closed die to produce a molding.
This process is similar to die casting of molten metals.
A plunger or a special screw mechanism applies pressure to force
the hot polymer into the die.
A wide variety of products, ranging from cups, combs, and gears to
garbage cans, can be produced in this manner.

Thermoplastic polymer sheets heated to the plastic region can be
formed over a die to produce such diverse products as egg cartons
and decorative panels.
The forming can be done using matching dies, a vacuum, or air

molten plastic is poured into a set of rolls with a small opening.
The rolls, which may be embossed with a pattern, squeeze out a
thin sheet of the polymeroften, polyvinyl chloride. Typical products
include vinyl oor tile and shower curtains.

Filaments, bers, and yarns may be produced by spinning.
The molten thermoplastic polymer is forced through a die containing
many tiny holes.
The die, called a spinnerette, can rotate and produce a yarn.
For some materials, including nylon, the ber may subsequently be
stretched to align the chains parallel to the axis of the ber; this
process increases the strength of the bers.

Many polymers can be cast into molds and permitted to solidify.
The molds may be plate glass for producing individual thick plastic
sheets or moving stainless steel belts for continuous casting of
thinner sheets.
Rotational molding is a special casting process in which molten
polymer is poured into a mold rotating about two axes.

placing the solid material before cross-linking into a heated die
Application of high pressure and temperature causes the polymer to
melt, ll the die, and immediately begin to harden
Small electrical housings as well as fenders, hoods, and side panels
for automobiles can be produced by this process

A double chamber is used in the transfer molding of thermosetting
The polymer is heated under pressure in one chamber.
After melting, the polymer is injected into the adjoining die cavity.
This process permits some of the advantages of injection molding to
be used for thermosetting polymers

Polymer application
Classification is based on end-use: plastics, elastomers, fibers, coating,
adhesive, foams & films.
Particular polymers may be used in more than 1 applications.

materials that have structural rigidity under load & use for general
purpose application
Polyethylene, polypropylene, PVC, polystyrene, epoxies
Some are very rigid, other are flexible exhibit elastic & plastic
deformation when stress, sometimes experiencing deformation
before fracture
Linear/branched must be used below glass transition T (if
amorphous) or below melting T (semicrystalline)

2) Elastomers rubbers
can be stretched to many times their original length, and can
bounce back into their original shape without permanent
include polyisoprene or natural rubber, polybutadiene,
polyisobutylene, and polyurethanes
Improving mechanical: crosslink structure
Silicon elastomers:
have a high degree of flexibility at low T (~90 C);
stable at T as high as 250 C
Biocompatible (blood tubing)


3) Fibers
long filament (L/D)=100:1
Mostly used in textile industry; woven or knit
Subjected to stretching, twisting, shearing & abrasion
high tensile strength, high modulus elastisity & abrasion resistance
high MW to be a strong material; will not break during drawing
linear structure with regular order
stable in various environments: acids, base, bleaches, dry cleaning
solvent & sunlight
relative nonflammable and amenable to drying

Miscellaneous Applications
Protect from corrosive/deteriorative reaction
Improve appearance
Provide electrical insulation
) Organic coaating:paint, varnish, enamel
) Many coating are latex (stable suspension
of small insoluble polymer particle disperse
in water); less organic solvent, less VOC
emission smog

substances used to bond 2 surfaces of solid material (adherends)
2 types of bond: mechanical & chemical
*Mechanical actual penetration of adhesive into surface pores &
*Chemical intermolecular forces between adhesive & adherend
Natural: casein, starch
Synthetic: polyurethanes, polysiloxanes, epoxies acrylic
Factors to choose adhesive:
1. Materials & porosities to be bond
2. Requires adhesive properties
3. T exposure environment
4. Processing conditions

Adhesive advantage over other joining technologies:

1. join dissimilar materials & thin components
2. lighter weight
3. better fatigue resistance
4. lower manufacturing cost
DrawbacksT limitation; maintain mechanical integrity only at low T,
strength decreases with increase in T
Used in aerospace, automotive, construction etc

Thin layer
0.025-0.125 mm thickness
Packaging, tape
Characteristic: low density, high
flexibility, high tensile & tear strength,
resistance to moisture & chemical, low
-permeability to some gases (water
polytethylene, polypropylene, cellulose

plastic material with high vol of
small pores & trapped gas
Thermoplastic &
thermosetting: polyurethane,
rubber, polystyrene
Cushion, thermal insulation
Bubbles are generated by
dissolving an inert into molten
polymer (high P); when P
reduce rapidly, the gas comes
out of solution & forms bubbles
& pores that remain in the solid
as it cools