DISCUSSION ON MATERIAL

LABORATORY ACTIVITY NO. 4

POLYMER

| ISIDRO | JOAQUIN | MAGNO | MERCULIO | PARAJAS | RACAL |

AGENDA:
•POLYMER STRUCTURES
•CHARACTERISTICS OF POLYMER
•TYPES OF POLYMER
•PROCESSES IN POLYMERS
•APPLICATION OF POLYMER
POLYMER
A polymer is a chemical
compound with large molecules made
of many smaller molecules of the
same kind. Some polymers exist
naturally and other are produced in
laboratories and factories.
POLYMER
structures
Hydrocarbon molecules
Most of the polymers are
originally from organic, we can
consider that polymers are
Hydrocarbon which means that
they are composed of hydrogen
and carbon.
Hydrocarbon molecules
A single covalent bond exists when each
of the two bonding atoms contributes
one electron.
 Hydrocarbon molecules
Double and triple bonds between two carbon
atoms involve the sharing of two and three pairs of
electrons.

NOTE:
Molecules that have double and triple covalent bonds are
called unsaturated and single covalent bonds are called
saturated.
Hydrocarbon molecules
ISOMERISM
is when compounds with the same
composition may have different atomic
arrangements
Hydrocarbon molecules
polymer molecules
The molecules in polymers are
gigantic in comparison to the
hydrocarbon molecules because of their
size they are often referred to as
macromolecules. Within each molecule,
the atoms are bound together by covalent
interatomic bonds.
polymer molecules
R and R’ represent
organic groups such as
CH3, C2H5, and C6H5
methyl, ethyl, and
phenyl
polymer molecules
Carbon Chain olymers
the backbone of each chain is a string of
carbon atoms. Many times each carbon atom
singly bonds to two adjacent carbon atoms on
either side, represented schematically in two
dimensions as follows
polymer molecules
Each of the two remaining valence
electrons for every carbon atom may
be involved in side bonding with atoms
or radicals that are positioned adjacent
to the adjacent to the chain. Both chain
and side double bonds are also
possible.
polymer molecules
REPEAT UNITS
these long molecules are
composed of structural entities,
which are successively
repeated along the chain
polymer molecules
MONOMER
small molecule from which a polymer is
synthesized
repeat unit is also sometimes called a
mer
from Greek word meros, which means
part
polymer was coined to mean
many mers
The chemistry of polymer molecules
Hydrocarbon thylene C2H4
is a gas at ambient temperature and
pressure
molecular structure
The chemistry of polymer molecules
POLYETHYLENE PE
transformation where the ethylene gas is
reacted under appropriate conditions
solid polymeric material
The chemistry of polymer molecules
The polymer chain then forms by the sequential
addition of monomer units to this active growing chain
molecule. The active site, or unpaired electron is transferred
to each successive end monomer as it is linked to the chain.
This may be represented schematically as follows
The chemistry of polymer molecules
Polyethylene Chain Structure
the final result, after the addition of many ethylene
monomer units, is the polyethylene molecule a portion
of one such molecule and the polyethylene repeat unit
this polyethylene chain structure can also be
represented as
The chemistry of polymer molecules
HOMOPOLYMER
when all of the repeating units along a
chain are of the same type

COPOLYMERS
chains may be composed of two or
more different repeat units
The chemistry of polymer molecules
BIFUNCTIONAL
are the monomers that have an
active bond that may react to form
two covalent bonds with other
monomers forming a two
dimensional chain like molecular
structure
The chemistry of polymer molecules
FUNCTIONALITY
is the number of bonds that a
given monomer can form

TRIFUNCTIONAL
have three active bonds, from which a
three dimensional molecular network
structure results
Molecular weight
Number average molecular weight
is obtained by dividing the chains into a series of
size ranges and then determining the number
fraction of chains within each size range
the number average molecular weight is
expressed as
Molecular weight
A weight average molecular weight
is based on the weight fraction of
molecules within the various size
ranges. It is calculated according to
Molecular weight
Degree of Polymerization, DP
an alternate way of expressing average chain
size of a polymer, which represents the
average number of repeat units in a chain
DP is related to the number average molecular
weight by the equation
Molecular weight
Molecular entanglements
occur when the chains assume
twisted, coiled, and kinked shapes
or contours as a consequence of
chain bond rotations. Rotational
flexibility is diminished when
double chain bonds are present,
and also when bulky side groups
are part of the repeat unit.
Molecular weight
Molecular shape
a A third carbon atom may lie at any point on the
cone of revolution and still subtend about a 109 angle
with the bond between the other two atoms.

b A straight chain segment results when successive

chain atoms are positioned.

c Chain bending and twisting are possible when there

is a rotation of the chain atoms into other positions.
Molecular shape
a. Linear Polymer
b. Branched Polymer
c. Cross Linked Polymer
d. Multifunctional
Monomers
Molecular shape
The term configuration is used
in reference to arrangements of units
along the axis of the chain, or atom
positions that are not alterable except
by the breaking and then re
forming of primary bonds.
Molecular configurations
STEREOISOMERISM
Denotes the situation in which atoms are linked
together in the same order (head to tail) but differ in their
spatial arrangement. For one stereoisomer, all of the R
groups are situated on the same side of the chain as
follows
Molecular configurations
ISOTACTIC CONFIGURATION
This diagram shows the zigzag pattern of the carbon
chain atoms. Furthermore, representation of the structural
geometry in three dimensions is important, as indicated by
the wedge shaped bonds solid wedges represent bonds that
project out of the plane of the page, and dashed ones
represent bonds that project into the page.
Molecular configurations
ATACTIC CONFIGURATION
The random positioning of
chained atoms.
Thermoplastic and thermosetting polymer
Thermoplastic polymers
have linear and branched structures they
soften when heated and harden when
cooled

Thermosetting polymers
once they have hardened, will not soften
upon heating their structures are
crosslinked and network
copolymers
copolymers
When calculating the degree of
polymerization for a copolymer, the
value m in equation below is replaced
with the average value that is
determined from
Polymer crystallinity
Polymer crystallinity is the packing of
molecular chains to produce an ordered
atomic array. Crystal structures may be
specified in terms of unit cells, which are
often quite complex.
Polymer crystallinity
The percent crystallinity of a
semicrystalline polymer is dependent on its
density as well as the densities of the totally
crystalline and totally amorphous materials
Polymer crystals
Crystalline Regions
or Crystallites
Plate shaped and have a
chain folded structure chains
within the platelet are aligned
and fold back and forth on
themselves, with folds
occurring at the faces.
Polymer crystals
SPHERULITE STRUCTURE
Many bulk polymers that are
crystallized from a melt are semi
crystalline and form a spherulite
structure. The spherulite consists of
an aggregate of ribbon like chain
folded crystallites (lamellae
approximately 10 nm thick that
radiate outward from a single
nucleation site in the center.
Defects in polymers
Diffusion in polymeric materials
With regard to diffusion in
polymers, small molecules of
foreign substances diffuse between
molecular chains by an interstitial
type mechanism from one void to
an adjacent one.
Diffusion in polymeric materials
Diffusion (or permeation of
gaseous species is often
characterized in terms of the
permeability coefficient, which is the
product of the diffusion coefficient
and solubility in the polymer.
Diffusion in polymeric materials
Permeation flow rates are
expressed using a modified form
of Fick s first law
Diffusion in polymeric materials
For small molecules in non glassy
polymers the permeability coefficient can be
approximated as the product of the
diffusion coefficient (D) and solubility of the
diffusing species in the polymer (S) that is,
Characteristics
Of polymer
Mechanical Behavior
of Polymers
A Stress-strain behavior

—
A Stress-strain behavior
A Stress-strain behavior
B Macroscopic Deformation
B Macroscopic Deformation
C Viscoelastic Deformation
C Viscoelastic Deformation
C Viscoelastic Deformation

—
 The viscoelastic behavior of
polymeric materials is dependent on
both time and temperature several
experimental techniques may be used
to measure and quantify this
behavior.
 Many polymeric materials are susceptible
to time dependent deformation when the stress
level is maintained constant such deformation
is termed viscoelastic creep. This type of
deformation may be significant even at room
temperature and under modest stresses that
lie below the yield strength of the material
D Fracture of Polymers
D Fracture of Polymers
D Fracture of Polymers
E Miscellaneous Mechanical
Characteristics
 The degree of resistance of a
polymeric material to impact loading
may be of concern in some
applications. Izod or Charpy tests are
ordinarily used to assess impact
strength.
 Polymers may experience
fatigue failure under conditions of
cyclic loading. As with metals,
fatigue occurs at stress levels that
are low relative to the yield strength.
 Other mechanical properties that are
sometimes influential in the suitability of a
polymer for some particular application
include tear resistance and hardness. The
ability to resist tearing is an important
property of some plastics, especially those
used for thin films in packaging.
Mechanical Behavior
of Polymers
 Many semicrystalline polymers in
bulk form have the spherulitic
structure. By way of review, each
spherulite consists of numerous
chainfolded ribbons, or lamellae, that
radiate outward from the center.
 Separating these lamellae are areas of
amorphous material, adjacent lamellae are
connected by tie chains that pass through
these amorphous regions.

1. Mechanism of Elastic Deformation

2. Mechanism of Plastic Deformation
 One of the fascinating properties of
the elastomeric materials is their
rubberlike elasticity. That is, they have
the ability to be deformed to quite
large deformations and then elastically
spring back to their original form.
 This results from crosslinks in the
polymer that provide a force to restore the
chains to their undeformed conformations.
Elastomeric behavior was probably first
observed in natural rubber however, the past
few years have brought about the synthesis
of a large number of elastomers with a
wide variety of properties.
I Vulcanization
The crosslinking process in
elastomers is called vulcanization,
which is achieved by a
nonreversible chemical reaction,
ordinarily carried out at an
elevated temperature.
I Vulcanization
types
Of polymer
plastic
plastic
plastic
plastic
plastic
ELASTOMERS
ELASTOMERS
FIBERS
coatings
adhesives
FILMS
Foams
1. Ultra-High-Molecular-Weight Polyethylene
2. Liquid Crystal Polymers
3. Thermoplastic Elastomers
Processes
in polymer
Crystallization,
Melting, and
Glass-Transition
Phenomena in Polymers
Crystallization
Crystallization is the process of
producing an ordered (i.e.
crystalline) solid phase from a
liquid melt with a highly random
molecular structure after it has
been cooled.
Crystallization
Crystallization
The overall kinetics for single
crystallization process in polymers,
which is controlled by nucleation
and growth, can be well described
by Avrami Equation.
Crystallization
Fraction crystallized y is a function of
time t, where k and n are time independent
constants, whose values depend on the
crystallizing system.

−𝑘𝑡 𝑛
𝑦=1
Crystallization
The crystallization of a molten polymer
occurs by nucleation and growth processes. For
polymers, upon cooling through the melting
temperature, nuclei form. These nuclei are
unstable because of atomic vibrations that tend
to disrupt the ordered molecular arrangements.
Rate of crystallization may be specified in the
same manner for the transformations.
Melting Tm= Melting Temperature
The melting transformation is the
reverse process that occurs when a
polymer is heated. The melting of a
polymer crystal corresponds to the
transformation of a solid material to a
viscous liquid.
Melting Tm= Melting Temperature
Glass Transition Tg= Glass Transition Temperature
The glass transition occurs in polymer
amorphous areas.
This phenomena corresponds to the
progressive transition of a liquid into a
rubbery material, and then to a stiff solid, as
it cools. The movement of huge portions of
molecular chains slows down as the
temperature drops.
Glass Transition Tg= Glass Transition Temperature
Melting and Glass Transition Temperatures
Melting and glass transition
temperatures are important parameters
relative to in service applications of
polymers. Tm and Tg also influence the
fabrication and processing procedures for
polymers and polymer matrix composites.
Melting and Glass Transition Temperatures
The behavior of semicrystalline polymers
that have the same configurations as their
ceramic counterparts. For the crystalline
material, there is a discontinuous change in
specific volume at the melting temperature Tm.
The totally amorphous material experiences a
decrease in slope at the glass transition
temperature, Tg.
Melting and Glass Transition Temperatures
Factors that Influence Melting and
Glass Transition Temperature:

Melting Temperatures
Glass Transition Temperature
In Melting Temperatures

Molecular chemistry and structure will

influence the ability of the polymer
chain molecules to make these
rearrangements and, therefore, will also
affect the melting temperature.
In Melting Temperatures

Chain stiffness, which is determined by the

ease with which chemical bonds throughout
the chain can be rotated, has a significant
impact. In the polymer backbone, the
presence of double bonds and aromatic
groups reduces chain flexibility and raises Tm.
In Melting Temperatures

The melting temperature of a

polymer will also depend on molecular
weight at relatively low molecular
weights, increasing (or chain length)
raises Tm.
In Glass Transition Temperature

Increasing the molecular

weight also tends to raise the
glass transition temperature.
In Glass Transition Temperature

A high density of branches

reduces chain mobility and elevates
the glass transition temperature. Some
amorphous polymers are crosslinked,
which has been observed to elevate Tg.
 Normally, the value of Tg is between
and Tm (in Kelvin). As a result, it is
impossible to change Tm and Tg
independently for a homopolymer. The
manufacture and use of copolymeric
materials allows for a better degree of
control over these two characteristics.
application
in polymer
POLYMER SYNTHESIS
AND
PROCESSING
1. Polymerization
Polymerization is the process of
linking monomers together to create
long chains made up of repeat units,
which is how these large molecules
(polymers) are made.
1. Polymerization
1. Polymerization
Coal, natural gas, and petroleum
products are the most common sources of
raw materials for synthetic polymers.
According to the reaction mechanism,
polymerization reactions are divided into
two categories addition and condensation.
I Addition Polymerization
The method of addition polymerization
also known as chain reaction polymerization
involves attaching monomer units one at a
time in a chainlike pattern to generate a linear
macromolecule. The final product molecule's
composition is an identical multiple of the
original reactant monomer's.
a. Initiation
b. Propagation
c. Termination
1. Combination
c. Termination
2. Disproportionation
II condensation Polymerization
The condensation polymerization is
the process by which polymers such
as nylon are produced. This stepwise
process is successively repeated,
producing a linear molecule.
II condensation Polymerization
2. Polymer additives
The majority of polymer qualities are
intrinsicones, or properties that are unique
to or fundamental to a particular
polymer. Many of these qualities are
enhanced or modified by the addition of
foreign compounds known as additives.
I Fillers
Filler materials are used to
improve the tensile and compressive
strength of polymers. Abrasion
resistance, toughness, dimensional
stability, and other qualities can all be
improved using them.
I Fillers
II Plasticizers
Plasticizers are additives that help
polymers become more flexible, ductile,
and tough. Hardness and stiffness are
also reduced as a result of their existence.
Plasticizers are typically liquids with low
molecular weights and low vapor pressure.
II Plasticizers
III Stabilizers
Under normal environmental
circumstances, some polymeric
materials deteriorate rapidly,
primarily in terms of mechanical
integrity. Stabilizers are additives that
slow down the deterioration process.
1. Exposure to ultraviolet (UV)
radiation causes one type of
degradation. This acts as a
sunscreen, preventing UV rays from
reaching the polymer and harming
the skin.
2. Oxidation is another key kind of
degradation, it is caused by the
chemical interaction of oxygen [as
diatomic oxygen or ozone
with the polymer molecules.
III Stabilizers
IV COLORANTS
Colorants are dyes or pigments
that are applied to a polymer to
give it a specific color. In a dye,
the molecules dissolve in the
polymer.
IV COLORANTS
Pigments are non dissolving
filler materials that have a tiny
particle size and a refractive index
close to that of the parent
polymer.
IV COLORANTS
V Flame Retardants
Flame retardant compounds can
improve the flammability resistance of
the remaining flammable polymers.
They work by interfering with the
combustion process in the gas phase, or
by initiating a new combustion reaction.
V Flame Retardants
3. Forming Techniques for Plastics

(1) whether the material is

thermoplastic or thermosetting
(2) if thermoplastic, the temperature
at which the stabilizer, colorant, or
flame retardant softens
3. Forming Techniques for Plastics

(3) the material's atmospheric stability;

(4) the geometry and size of the finished
product. Some of these procedures are
remarkably similar to those employed in
the fabrication of metals and ceramics.
3. Forming Techniques for Plastics
The fabrication of polymeric materials
is usually done at high temperatures and
with a lot of pressure. Amorphous
thermoplastics are formed above their glass
transition temperatures, while semicrystalline
thermoplastics are formed above their
melting temperatures.
3. Forming Techniques for Plastics

The first step is to make a linear

polymer (also known as a prepolymer)
as a low-molecular-weight liquid. During
the second stage, this material is
transformed into the final hard and stiff
product, which is usually done in a mold
with the desired shape.
3. Forming Techniques for Plastics
This second stage, referred to as curing,
can take place while the product is being
heated and/or catalysts are being added,
and it is frequently done under pressure.
On a molecular level, curing causes
chemical and structural changes, resulting
in the formation of a crosslinked or
network structure.
3. Forming Techniques for Plastics
Because thermoset polymers are now
dimensionally stable after curing, they can
be removed from a mold while still hot.
Thermosets are difficult to recycle, do not
melt, may be used at greater temperatures,
and are frequently more chemically inert
than thermoplastics.
I molding
The most popular method for
producing plastic polymers is molding.
Compression, transfer, blow, injection,
and extrusion molding are among the
molding techniques employed.
I molding
 This molding technique may be used
to make both thermoplastic and
thermosetting polymers. The solid
materials are first melted in a heated
transfer chamber in transfer molding, a
form of compression molding. The
pressure is distributed more consistently.
 Polymer granules are crushed by a ram
or screw, heated until molten, then squirted
into a cold, split mold under pressure in
injection molding. The formed polymer is
cooled below TG, the mold opens and the
product is expelled. Excess polymer is injected
to compensate for contraction in the mold.
 Extrusion is a technique where
molten polymer is forced through a
die and is used to produce
components of a fixed cross sectional
area such as tubes and rods.
 Plastic containers are made
using a blow molding method
similar to that used to make
glass bottles.
 Polymeric materials, like metals,
can be cast by pouring molten plastic
into a mold and allowing it to harden.
Casting is possible with both
thermoplastic and thermosetting
polymers.
4. Fabrication of Elastomers
Techniques used in the actual
fabrication of rubber parts are
essentially the same as those
discussed for plastics as described
previously that is, compression
molding, extrusion, and so on.
4. Fabrication of Elastomers
5. Fabrication of Fibers and Films
Spinning is the technique of
forming fibers from bulk
polymer material. Melt spinning
is a method of spinning fibers
from a molten state.
Two Methods of Manufacturing Fibers
Dry Spinning
Dry Spinning
Two Methods of Manufacturing Fibers
Wet Spinning
Wet Spinning
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