Teknologi Material Baru

Dr. Aprilina Purbasari, ST, MT

Polymers
Polymer is a large molecule built up by the repetition of small, simple chemical
units.

General characteristics of polymers:

• Polymers have long chain structures. The individual molecule of a polymer is
very large, i.e., it may consists of thousands of similar small molecules, all
bonded together covalently.
• All polymers have one thing common, i.e., carbon, which further bonds with
hydrogen, nitrogen, halogens or other organic or inorganic substances.
• Although, polymer’s structure may be crystalline in simple materials but
generally they are non-crystalline solids at room temperatures.
• Polymers have light weight and they can be easily fabricated and shaped.
• They are poor conductors of electricity and their thermal conductivity is also
low.
• The polymers are resistant to chemical attack and decay.
Common polymeric materials
Polymerization Process
• Polymerization, or the joining of large unit molecules called
monomers, utilizes the valence of the partially filled outer shell of the
carbon atom (carbon has a valence of 4) to join smaller units together
to form larger chains of molecules. Oxygen, sulphur, silicon, or
nitrogen can be used to replace the carbon atom.

• Polymerization takes place through addition polymerization,

copolymerization, or condensation polymerization.

• In the polymerization process, a large unit molecule, the monomer, is

added to another monomer to form a large chain, the polymer
(referring to many parts), which has a number of repeated units, mers.

• Mers are the smallest units recognizable in the chain.

• Addition polymerization involves only one type of
mer.
• In copolymerization, more than one molecule makes
up the mer. Acrylonitride-butadiene-styrene (ABS) is
an example of a copolymer.
• Condensation polymerization involves the chemical
reaction of two or more chemicals to form a new
molecule. This chemical reaction produces a
condensate or nonpolymerizable by product, usually
water. A catalyst is often required to start and
maintain the reaction. It can also be used to control
the reaction rate.
Degree of polymerization

where:
• DP = degree of polymerization (the number of repetitions of
mers in a polymer chain)
• = the number-average molecular weight
• m = the repeat unit molecular weight
• xi = the fraction of the total number of chains within the
corresponding size range
• Mi = the mean (middle) molecular weight of size range i
Molecular structures of polymer

• Polymers are not usually of only one distinctive structural type. For example,
a predominantly linear polymer might have limited branching and
crosslinking.
Linear Polymers

• Linear polymers are those in which the repeat units

are joined together end to end in single chains.
• These long chains are flexible.
• For linear polymers, there may be extensive van der
Waals and hydrogen bonding between the chains.
• Some of the common polymers that form with linear
structures are polyethylene, poly(vinyl chloride),
polystyrene, poly(methyl methacrylate), nylon, and
the fluorocarbons.
Branched Polymers

• Polymers may be synthesized in which side-branch chains are

connected to the main ones, these are fittingly called branched
polymers.
• The branches, considered to be part of the main-chain molecule,
may result from side reactions that occur during the synthesis of
the polymer.
• 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.
• For example, high density polyethylene (HDPE) is primarily a
linear polymer, while low density polyethylene (LDPE) contains
short chain branches.
Crosslinked Polymers

• In crosslinked polymers, adjacent linear chains are

joined one to another at various positions by covalent
bonds.
• The process of crosslinking is achieved either during
synthesis or by a nonreversible chemical reaction.
• Often, this crosslinking is accomplished by additive
atoms or molecules that are covalently bonded to
the chains.
• Many of the rubber elastic materials are crosslinked;
in rubbers, this is called vulcanization.
Network Polymers

• Multifunctional monomers forming three or more

active covalent bonds, make three-dimensional
networks and are termed network polymers.
• Actually, a polymer that is highly crosslinked may
also be classified as a network polymer.
• These materials have distinctive mechanical and
thermal properties.
• The epoxies, polyurethanes, and phenol-
formaldehyde belong to this group.
Molecular configurations of polymer
Stereoisomerism
• Stereoisomerism denotes the situation in which atoms are linked
together in the same order (head-to-tail) but differ in their spatial
arrangement.
• Isotactic configuration: all the R groups are situated on the same
side of the chain.
• Syndiotactic configuration: the R groups alternate sides of the
chain.

• Atactic configuration: the R groups in random positioning.

• In reality, a specific polymer does not exhibit just one of these

configurations; the predominant form depends on the method of
synthesis.
Geometrical Isomerism
• Geometrical isomers are chain configurations which repeat units
having a double bond between chain carbon atoms.
• Bonded to each of the carbon atoms participating in the double
bond is a side group, which may be situated on one side of the
chain or its opposite.
• The isoprene repeat unit haves the structure in which the CH3
group and the H atom are positioned on the same side of the
double bond.

• This is termed a cis structure, and the resulting polymer, cis-

polyisoprene, is natural rubber.
• For the alternative isomer the trans structure, the CH3 and H
reside on opposite sides of the double bond.

• Trans-polyisoprene, sometimes called gutta percha, has

properties that are distinctly different from natural rubber as
a result of this configurational alteration.
• Conversion of trans to cis, or vice versa, is not possible by a
simple chain bond rotation because the chain double bond is
extremely rigid.
 Usually polymers are broadly classified in
three categories:
• Plastics
• Fibres
• Elastomers.
Plastics
• These are the organic materials that can be easily shaped or moulded
by mechanical or chemical action, with or without the application of
heat.
• Polyethylene, polypropylene, polyvinyl chloride, polystyrene,
fluorocarbons, epoxies, phenolics and polyesters may be put under this
category.
• Plastics have a wide variety of combination of properties. There are
some plastics which are very rigid and brittle, whereas others are
flexible, exhibiting both elastic and plastic deformations when stressed,
and some time experiencing sufficient deformation prior to fracture.
• Polymers belonging to this class of materials may have any degree of
crystallinity, and all molecular structures and configurations (i.e., linear,
branched, isotactic, etc.) are possible.
Plastics have following properties:
• Plastics are light weight materials that is their densities and specific
gravities are low.
• They have high resistance to chemical attack, i.e. corrosion.
• They have very good surface finish when obtained from the dies.
• They have high thermal and electrical insulation.
• As compared to metals their strength is low and also low elastic
modulus value.
• As compared to metals, plastic have low softening and thermal
degradation temperature.
• Plastics are poor to fair dimensional stability, particularly in moist
conditions.
• Plastics are available in different colours as well as transparent form.
• With respect to metals, plastics have high coefficient of thermal
expansion.
• These are unsuitable for high temperature applications.
• Plastics can be easily fabricated.
There are many plastics with outstanding properties:
• Polystyrene and polymethyl methacrylate are especially
useful for applications in which optical transparency is
critical, however, it is imperative that the material be
highly amorphous or, if semicrystalline, have very small
crystallites.

• The fluorocarbons have a very low coefficient of friction

and moreover they are extremely resistant to attack by a
host of chemicals, even at relatively high temperatures.
They find wide range of uses as coatings. On nonstick
cookware, in bearings and bushings, and for high
temperature electronic components.
 Plastic materials may further be classified as thermoplastic or
thermosetting:
• Thermoplastics are generally referred to as plastics and have
the property of increasing plasticity, i.e., ability to deform
plastically with rise in temperature. They have the long chain
structure.
• On the otherhand, thermosetting plastics have the three
dimensional network of primary bonds. On heating they do
not get soft. When heated, they become harder due to
completion of any left over polymerization reaction. Due to
their reaction with atmospheric air, they get decomposed at
high temperatures. The process of decomposition in respect
of thermosetting plastic is called degradation.
(a)Thermoplastics and (b) thermosets plastics
Plastics
Fibres
• These consists of long molecular chains and all the chains are
aligned in the direction of length of the fibre. The directional
properties are improved by alignment, i.e. the strength of
fibres are greatly enhanced in the direction parallel to the
fibre length.
• The fibre polymers are quite capable of being drawn into long
filaments having at least a 100 : 1 length to diameter ratio.
• Some polymers used as fibres, such as nylon and cellulose
acetate, serve equally well as plastics.
• Most commercial fibre polymers are utilized in the textile
industry, being woven or knit into cloth or fabric.
• Fibres, while is use may be subjected to a variety of
mechanical deformations, e.g. stretching, twisting,
shearing and abrasion.
• Fibres materials should have relatively high molecular
weight. The structure and configuration of the chains
should allow the production of a highly crystalline
polymer as the tensile strength increases with degree of
crystallinity.
• Synthetic fibres are produced by the following methods:
melt spinning, dry spinning and wet spinning. To
improve fibres properties, i.e., to increase/decrease
resistance, water or fire proofs, etc., chemical treatment
is done.
• The thermal properties of fibre polymers are important from
the point of view of washing and maintaining clothes. These
properties include melting and glass transition temperatures.
• Also, fibre polymers must show chemical stability to a rather
extensive variety of environments, including acids, bases, dry
cleaning solvents, bleaches, and sunlight. Moreover, they
must be relatively non flammable and amenable to drying.
• There are natural fibres, e.g. cotton, silk, wool, cellulose, etc.
Cellulose fibres are flexible and are strong in tension. Cotton
is produced naturally as a plant fibre.
• The synthetic fibres are cheap, durable and have more
dimensional stability and that is why they have almost
replaced the natural fibres.
Synthetic fibres
Elastomers
• These are also long chain molecules, but exhibit the
unique property of high elasticity.
• These materials may be repeated stretched or
elongated and will return to their original condition
upon release of the force producing the elongation.
• They, exhibit elastic behaviour, as compared to
polymers, which exhibit greater plastic properties.
• Included in this category are rubber and rubber like
materials.
• This property of a material to recover from elastic
deformation is termed as resilience.
 There are several criteria which have to be met for a polymer
to be elastomeric:
• It must be easily crystallize. We may note that elastomeric
materials are amorphous, having molecular chains that are
naturally coiled and linked in the unstressed state,
• For the coiled chains, chain bond rotations must be relatively
free so that they may readily respond to an applied force,
• To experience relatively large elastic deformations for
elastomers, the onset of the plastic deformation must be
delayed. This objective is achieved by restricting the motions
of chains past one another by crosslinking. The crosslinks acts
as anchor points between the chains and prevent chain
slippage to occur. In many elastomers, crosslinking is carried
out in a process called vulcanization.
• The elastomer must be above its glass transition temperature.
• The lowest temperatures at which rubber like
behaviour persists for good number of common
elastomers is between –50 and –90°C.
• An elastomer becomes brittle below its glass transition
temperature.
• The properties of common elastomers are typical and,
of course, depend on the degree of vulcanization and
on whether any reinforcement used.
• Natural rubber has an outstanding combination of
desirable properties and still utilized to a large degree.
• The most important synthetic elastomer is SBR
(styrene butadiene copolymer) which is used especially
in automobile tyres, reinforced with carbon black.
Vulcanization
• Vulcanization is the crosslinking process in elastomers, which
is achieved by a non reversible chemical reaction, ordinarily
carried out at an elevated temperature.
• In several vulcanizing reactions, sulphur compounds are
added to the heated elastomer.

• Main chain sites of crosslink are carbon atoms that were

doubly bonded prior to vulcanization but, after vulcanization,
have become singly bonded.
• Modulus of elasticity, tensile strength, and resistance to
degradation by oxidation all are enhanced by this technique.
• The sulphur content controls the number of anchoring
points. The magnitude of the modulus of elasticity is
directly proportional to the density of the crosslinks.

• One obtains the useful rubber when about 1 to 5 parts (by

weight) of sulphur are added to 100 parts of rubber.
Thermoplastic elastomers
• Thermoplastic elastomers, sometimes referred to as elastoplastics,
result from the copolymerization of two or more monomers.
• One monomer is used to provide the hard, crystalline features,
whereas the other monomer produces the soft, amorphous features.
• When combined, these form a thermoplastic material that exhibits
properties similar to the harder, vulcanized elastomers.
• Thermoplastic elastomers can be either molded or extruded into
finished shapes.
• Urethanes were the first thermoplastic elastomers to be
produced. These products are used in such applications as
gaskets, gears, and fuel lines.
• Other thermoplastic elastomers include copolyester, styrene,
and the olefins.
• Copolyester elastomers have more properties but are more
expensive than urethanes. They are used as hydraulic hoses,
couplings, and cable insulation.
• Styrene copolymers are less expensive than either urethanes
or copolyesters. They have a lower tensile strength but exhibit
greater elongation. SBR is used in medical products, tubing,
packaging materials, adhesives, and sealants.
• Thermoplastic olefins (TPO) are used in tubing, seals, gaskets,
and electrical products.
Polyurethane elastomers