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Of polymers
CRYSTALLINITY
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
semicrystalline)
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.
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
layers
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
SYNTHESIS
Stages in polymer synthesis:
1) Polymerisation synthesize macromolecules from small
ones
2) additive materials modifie & enhance the properties
3) finishing pieces fashione & shape product
POLYMERISATION
monomers are linked together to generate long chains
1) Addition polymerization
Chain reaction polymerization through free radical polymerisation
i)
Initiation
)
)
ii) Propagation
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
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
reaction.
H2O is eliminated in the
reaction.
General reaction between a
dicarboxylic acid and a diol:
POLYMER ADDITIVES
Additives substances introduce to enhance/modify
properties, thus more serviceable: plasticizers,
stabilizers, colorants, flame retardants, fillers
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
PLASTISIZER
-
STABILIZERS
- Additive to counteract deterioration in some polymers
under normal environment expose to light-UV &
oxidation
# 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
damage
#
Colorants
- give color to polymer
- added as dyes
- molecules dyes dissolve in
polymer
-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
flammable
- used in textile & toys
- interfere the combustion
process by initiating
different combustion
reaction generate less
heat, reduce T slowing
burning
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.
BLOW MOLDING
A hollow preform of a thermoplastic called a parison is introduced
into a die by gas pressure and expanded against the walls of the
die.
This process is used to produce plastic bottles, containers,
automotive fuel tanks, and other hollow shapes.
EXTRUSION
INJECTION MOLD
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.
THERMOFORMING
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
pressure.
CALENDARING
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.
SPINNING
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.
CASTING
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.
COMPRESSION MOLDING
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
TRANSFER MOLDING
A double chamber is used in the transfer molding of thermosetting
polymers.
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.
1) PLASTICS
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
deformation.
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)
ELASTOMERS (rubber)
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
COATING
Function:
1)
Protect from corrosive/deteriorative reaction
2)
Improve appearance
3)
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
ADHESIVES
substances used to bond 2 surfaces of solid material (adherends)
2 types of bond: mechanical & chemical
*Mechanical actual penetration of adhesive into surface pores &
crevices
*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
FILMS
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
vapor)
polytethylene, polypropylene, cellulose
acetate
FOAMS
plastic material with high vol of
small pores & trapped gas
bubble
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