Assignment

Polymers, Thermoplastics and

Thermosetting Plastics

Member of Group :
1. Melisa Permata Rosha (2613161018)
2. Redi Sabihisani Wijaksono (2613161029)
3. Moch Fargan S.M (2613161001)
4. Billy Rabani Tanjung (2613161030)

Jenderal Achmad Yani University

Faculty of Engineering
Metallurgical Engineering
POLYMER STRUCTURES

What is it Polymer?
Naturally occurring polymersthose derived from plants and animalshave been
used for many centuries; these materials include wood, rubber, cotton, wool,
leather, and silk. Other natural polymers such as proteins,enzymes,starches,and
cellulose are important in biological and physiological processes in plants and animals.
Modern scientific research tools have made possible the determination of
the molecular structures of this group of materials,and the development of ngbt`umerous
polymers, which are synthesized from small organic molecules.Many of
our useful plastics, rubbers, and fiber materials are synthetic polymers. In fact, since
the conclusion of World War II, the field of materials has been virtually revolutionized
by the advent of synthetic polymers. The synthetics can be produced
inexpensively, and their properties may be managed to the degree that many are
superior to their natural counterparts. In some applications metal and wood parts
have been replaced by plastics, which have satisfactory properties and may be produced
at a lower cost.
As with metals and ceramics, the properties of polymers are intricately related
to the structural elements of the material.This chapter explores molecular and crystal
structures of polymers;
Have you ever ridden a bicycle or even a motorcycle? An essential part of the bike is the
chain, which drives the back wheel. Chains are widely used in machinery and even jewelry,
such as a bracelet or necklace. All chains share in common a structure made of links. These
links are repeated units with similar or identical structure joined in some way. Think of a long
train with many similar cars.
Linked chains are also important in chemistry. A polymer is a chain of repeated units. The
word comes from the Greek, polu meaning 'many' and meros meaning 'share.' The units that
make up polymers are called monomers. The unit of most natural polymers is typically an
'organic molecule', therefore containing carbon - the stuff you, me and all living things are
made of.

Polymer Molecules
The molecules in polymers are gigantic in comparison to the hydrocarbon molecules
already discussed; because of their size they are often referred to as macromolecules.
Within each molecule, the atoms are bound together by covalent interatomic bonds.
For carbon chain polymers, the backbone of each chain is a string of carbon atoms.
Many times each carbon atom singly bonds to two adjacent carbons atoms on either
Side.
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
chain. Of course, both chain and side double bonds are also possible.
These long molecules are composed of structural entities called repeat units,
which are successively repeated along the chain.1 The term monomer refers to the
small molecule from which a polymer is synthesized. Hence, monomer and repeat
unit mean different things, but sometimes the term monomer or monomer unit is
used instead of the more proper term repeat unit.
NATURAL POLYMERS
Years ago, before there were plastics and synthetic polymers, in fact, all the way back to the
beginning of the earth, nature was using natural polymers to make life possible. We don't
think of natural polymers in the same way as synthetic polymers because we can't take credit
for them as marvels of our own ingenuity, and chemical companies can't sell them for profit.
However, that doesn't make natural polymers less important; it turns out in fact, that they are
more important in many ways.

Natural polymers include the RNA and DNA that are so important in genes and life
processes. In fact, messenger RNA is what makes possible proteins, peptides, and enzymes.
Enzymes help do the chemistry inside living organisms and peptides make up some of the
more interesting structural components of skin, hair, and even the horns of rhinos. Other
natural polymers include polysaccharides (sugar polymers) and polypeptides like silk,
keratin, and hair. Natural rubber is, naturally a natural polymer also, made from just carbon
and hydrogen. Let's look at each of the main families of natural polymers closely.

Polysaccharides
DNA and RNA
RNA and DNA contains polymer backbones which are based on sugar units. This makes
them polysaccharides, although in the case of RNA and DNA, there are well ordered groups
attached to the sugar units that give these polymers their unique capabilities.

Wood and Potatoes

Another family of polysaccharides includes starch and cellulose. Starch is a high molecular
weight polysaccharide. Foods like bread, corn, and potatoes are full of starch. Starch may
have as many as 10,000 sugar units all linked together. The way these units link up, all in a
linear arrangement or with some of
them forming branches, determines
what kind of starch or polysaccharide
it is (more about this later). Another
very important member of the
polysaccharide family is cellulose.
This is the main polymer that makes
up plants and trees. Wood is primarily
cellulose This polymer is different than starch. (Click here to find out more.) Starch is soluble
n hot water and can easily be made into useful objects. Cellulose, on the other hand, is
highly crystalline and almost totally insoluble in anything. Cotton is a form of cellulose that
we use in most of our clothes. The fact that it is insoluble in hot water is important. Were it
otherwise our clothes would dissolve when we washed them. Cellulose also has the neat
property that when you wet it and run a hot iron over it, it smoothes out and flattens down.
This makes our cotton clothes look nice (at least for a little while) but still allows them to
clean up easily when we wash them.

Chitin: The Polymer for the Seafood Lover in You!

Another member of the polysaccharides is
chitin. It makes up the shells of crawfish,
shrimp, crabs, lobsters, and other crustaceans.
It is hard, insolubleand yet somehow
flexible. We haven't figured out how to make
synthetic polymers that have this neat
combination of properties. We also haven't
figured out how to do much with chitin,
although we do use cellulose for a lot of chemical applications and to make paper, wooden
houses, wooden shoes, and the like. There's a lot of research underway to use chitin for
different stuff, and maybe someday we'll make clothes or plastic out of it. This is an area of
research that its important since it uses natural polymers that come from renewable resources
or waste products. (Do you know how many shrimp lose their shells every year for us?)

Chemically, chitin is poly(N-acetylglucosamine). Here's it's structure:

We Learn from Nature

As you take a look more closely at each member of these families of natural polymers,
remember this: nature was there first, by a long shot! One of our jobs as scientists is to figure
out how nature does such a good job so that we can imitate it. For example, once we figured
why silk had such neat properties we were able to make synthetic silk in the form of nylons.
We still have a long way to go, though, before we can make synthetic RNA and DNA that
will lead to synthetic life. While we may never get there, trying to figure out how is fun and
leads to lots of important developments in synthetic polymers and other areas including
medicine and biochemistry. This raises the important point that science is like life. It doesn't
deal with just one thing, but everything mixed together. Polymer science isn't the only
science, and it may not even be the most important science (although we in the business like
to think it is!). It is one of the areas that can help us understand and use the knowledge we get
from studying nature. In this way, we develop technology.

(Note: Just to clear up this whole science-and-technology question, science and technology
are two different things. Science is the act of gathering knowledge by observation and
experimentation. Technology is putting this knowledge to use. Example: Using science we
learn that hot gasses expand. Then using technology, we use the principle hot gasses
expanding to make a gasoline engine that can power a car. See how it works?)

Proteins and Polypeptides

Proteins
Proteins were the first examples of polyamides (a fancy word for nylon). Both share many
common traits but they are very different in how they are made and in their physical
properties. They are alike in that the both contain amide linkages in the backbone. Amides are
made from carboxylic acid groups and amine groups through the loss of water. (For more on
this clickhere.) The amide molecular segment is unique in its structure and intermolecular
interactions. Because of the hybridization of the nitrogen, carbon, and oxygen of the amide
group, the segment is basically flat. More importantly, the hydrogen on the nitrogen and the
carbonyl oxygen are capable of a strong interaction called a hydrogen bond. Because of this,
the amide groups like each other some much that they for strong associations that give amide-
containing polymers unusual properties. This type of interaction is also discussed in the
section on nylons, and is the key similarity between natural and synthetic polyamides.

The differences between how nature does nylons and how we do it is striking.We mostly
make nylons from molecules that have lots of CH 2 groups in them.The section on nylons
shows structures for nylon 6 and nylon 6,6, two of the most common synthetic polyamides.
They possess four, five, or six CH 2 groups between amide units. Nature, however, is much
more economical, choosing to use only a single carbon between amide groups. What nature
does differently is to substitute this carbon with lots of different functional segments and
groups.
This results in two key properties. First, the individual segments and the entire molecule are
optically active, or chiral. This means they are like gloves: there are both right and left and
versions. For some reason, nature chose to use only the left hand version of the amino acids
that are synthesized by plants and animals. The fact that only one of the two isomers is used
leads to some neat stereochemical consequences. For example, natural polypeptides can form
helical structures while nylons can't. The helical conformations increase the stability of the
natural polypeptides. Did you know that some bacteria can survive in boiling water? This is
because their natural polymers have been stabilized by such helical structures. The figure
below shows one such helical structure, called an a-helix. Small segments of such helical
structures are what nature uses to mold enzymes into certain shapes so that they can do their
catalytic magic. For example, a flexible randomly coiled segment may be joined by two a-
helix segments so that they can react together on some substrate.

Enzymes
Enzymes are one of the key types of polypeptides and are crucial to life on earth. All living
organisms use enzymes to make, modify, and chop up the polymers discussed here. Enzymes
are the catalysts that do specific jobs. In fact, oftentimes each enzyme does only one type of
job or makes only one kind of molecule. This means that there have to be lots of different
enzymes, all made of different combinations of amino acids joined in unique ways in
polypeptides, to do all the jobs that any living organism needs done. We know that every
creature on earth has hundreds or even thousands of different enzymes to do all the jobs that
it requires. What's really strange is that each one of the enzymes has to be made by other
enzymes. This leads to very complicated control mechanisms: we don't have the faintest idea
(in most cases) how nature decides what enzymes need to be made and when, or how the
enzymes are turned on and off. We are beginning to figure this out, and the study of such
systems is an important part of biochemistry and biology.

Riding Down the Silk Road

One of the unique polypeptides that we used very early for its superb properties was silk. Silk
was discovered by the Chinese long before the birth of Christ. Silk is made by tiny
caterpillars trying to spin cocoons for their transformation into moths. We steal the silk from
the caterpillars which leaves them in limbo, pretty much. The silk is spun into fibers. Bundles
of very thin individual polymers joined together to be stronger. This is the way we also make
rope, using weak individual strands bound together in such a way that the total is both
flexible and strong. The structure of silk molecules is unusual for a polypeptide. It possesses
lots of the unsubstituted amino acid, glycine. Glycine segments are able to form flat extended
chains that can pack together nice and tightly. This gives silk its unique strength and shiny
flexibility. Silk has such unique properties, especially in hot wet climates, that it dominated
trade for centuries in east Asia. The silk trade between Japan and China controlled the
economics of civilizations in that region for longer than either country cares to admit. Even in
America, silk was important before World War II for use in silk stockings. When silk was
used for parachute cord, women in America got very upset. This resulted in chemical
companies synthesizing artificial silk, nylon, to make nylon stockings so that women's feet
could stay warm and the men could go back to fighting their wars.

Another key difference between polypeptides and nylons is the way they are made. We
humans make nylons in tons per day in huge chemical plants where simple molecules are
joined together in large quantities to give products that we need or want. Nature is much more
careful and concise in how she does things. For a living organism to make an enzyme,
another enzyme or active species must be involved. The synthesis always involves a template,
or recording, of how the individual amino acids are to be joined together to give the final
polymer. This template, or map is a messenger RNA (mRNA). The message it carries, of
course, is how the peptide-making enzyme involved should make the polypeptide. Each
amino acid is brought to the enzyme by a carrier molecule and is activated for incorporation
by a whole cascade family of reaction steps. The enzyme adds a single amino acid, one at a
time, as indicated by the mRNA. This is a slow and tedious process and takes a long time.
Sometimes the enzyme gets frustrated, waiting for the right amino acid to come along, and
slaps a wrong one on instead. To compensate this the enzyme is made to back up occasionally
to check its work. If it has made a mistake, it has a process for clipping out the wrong amino
acid and inserting the right one. We humans never do this. If we make a mistake, we simply
grind it up and throw it away.

Our Feeble Capabilities

We are beginning to understand how nature puts these molecules together and we've figured
out how to do it ourselves. However, we're not very good at it and can't make very large
molecules vary efficiently. The reason is, if we make a mistake, it ruins the whole molecule
and we don't know how to fix it. The kind of machine that's used to make synthetic analogs of
polypeptides is called a "peptide synthesizer". Such a machine is built around tiny polymer
beads that we attach to the first amino acid which we want to put in our polypeptide chain.
(This is called the Merrifield Synthesis Approach. The use of polymer beads was a great
creative idea, and Robert Merrifield won the Nobel Prize for it back in 1984.) We than take
an activated amino acid, similar to what nature uses, and attach it by forming an amide bond.
We repeat this process over and over again, trying to get this reaction to go every time on
every molecule on every bead. Sometimes, we are not so lucky and we miss and amino acid.
This means that some of the polypeptides have units missing. This always leads to mixtures
of good product and bad product, in which the good product may be the minor component.
This gets worse the bigger the polypeptide we are trying to make, and is one of the major
problems we have with how we make polypeptides. If we could just figure out how to back
up and check each one of our additions, and then correct the mistakes that are there, maybe
we could do as good a job as nature. Maybe.

You're probably asking why we would want to do such a bad job of making synthetic analogs
of what nature does so well. (If you aren't, just play along anyway.) There are lots of reasons,
one of which is to figure out just how nature does it. Another is to figure out why peptides
and enzymes work the way that they do. It's not always clear to us mere mortals why a given
sequence of amino acids causes a polypeptide to assume a certain shape or structure. These
structures are key to how the polypeptides do whatever job nature has devised for them.
Sometimes, when we see the way nature puts these molecules together, we can make
synthetic analogs that do the same thing but are easier to make. This has led to the
development of new drugs and to treatments for some genetic diseases.

Nature also does things differently than us by synthesizing polypeptides in water. Most of our
syntheses, in fact, don't use water. We synthesize our polyamides in toxic organic solvents.
This leads us to a problem: what do we do with the organic solvents when we're through?
Sometimes we burn the, but more and more we try to recycle these materials. Not only are
they getting more expensive to buy in the first place (compared to cheap water which is
everywhere, or almost everywhere) but we must be responsible for their recycle, purification,
and final disposal. An example of how nature uses water in this way, and one which we still
haven't figured out is the production of spider silk. Spiders spin their webs from solutions of
polypeptides in water. These solutions are squeezed through the spider's tiny spinneret and
elongated quickly to form the spider webs which we've all seen and sometimes gotten tangled
in. What's really weird is that, once these spider webs form, they are no longer soluble in
water. If we could just figure out how spiders first make spider silk in water and then spin
their webs from it, we could make nylon the same way. This might save us a lot of waste
disposal problems, and money. This is one area of basic research where we need lots and lots
of help; maybe you can think of something we could try.

Natural vs Synthetic Polymers

There are two types of polymers: synthetic and natural. Synthetic polymers are derived from
petroleum oil, and made by scientists and engineers. Examples of synthetic polymers include
nylon, polyethylene, polyester, Teflon, and epoxy. Natural polymers occur in nature and can
be extracted. They are often water-based. Examples of naturally occurring polymers are silk,
wool,DNA,cellulose and proteins.
In our previous section on network polymers, we mentioned vulcanized rubber and pectin.
Vulcanized rubber is a synthetic (man-made) polymer, while pectin is an example of a natural
polymer.

Rubber can be found in nature and harvested as a latex (milky liquid) from several types of
trees. Natural rubber coming from tree latex is essentially a polymer made from isoprene
units with a small percentage of impurities in it. Rubber can also be made (synthesized) by
man. Synthetic rubber can be made from the polymerization of a variety of monomers,
including isoprene.

Natural rubber does not handle easily (it's sticky), nor does it have very good properties or
durability (it rots). It is usually vulcanized, a process by which the rubber is heated in the
presence of Sulfur, to improve its resilience, elasticity and durability. Synthetic rubber is
preferable because different monomers can be mixed in various proportions resulting in a
wide range of physical, mechanical, and chemical properties. The monomers can be produced
pure and addition of impurities or additives can be controlled by design to give optimal
properties.

Vulcanization, also called curing, is the chemical process used in the rubber industry in which
individual polyisoprene chains are linked to other polyisoprene chains by chemical bonds
(see reaction sequence below). The actual chemical cross-linking is usually done with Sulfur,
but there are other technologies that can also be used. Vulcanization is an irreversible process,
like baking a cake. The normally soft and springy rubber molecules become locked together
resulting in a harder material with greater durability and chemical resistance. Vulcanization
changes the surface of the material from very sticky to a smooth, soft surface which does not
adhere to metal or plastic substrates.

Source: www.chemistrydaily.com.

Pectin is a long chain polymer composed of pectic acid and pectinic acid molecules (see
structure below). Because these acids are sugars, pectin is called a polysaccharide. It is
obtained from citrus peels and the remains of apples. In the plant/fruit, pectin is the material
that joins the plant cells together.

Source: www.cybercolloids.net.

The pectin chains form a network because some of the segments of the pectin chains join
together by crystallization to form a three-dimensional network in which water, sugar and
other materials are held. Formation of a gel is caused by physical or chemical changes that
tend to decrease the solubility of the pectin and this favors the formation of small localized
crystals. The most important factor which influences pectin's tendency to gel is temperature.

When cooling a hot solution containing pectin, the movement of the molecules is decreased
and their tendency to combine into a gel network is increased. This ability makes pectin a
good thickener for many food products, like jellies and jams. If there is sufficient sugar in the
mixture, pectin forms a firm gel.

Types of Polymers
Polymers form by the process of polymerization, where monomers link together to form the
chain, like linking pearls on a string. Polymerization usually occurs only in the presence of
acatalyst. The units of polymers can be simple or complex. The length of a polymer chain can
be long or short. Chemists recognize two main categories of polymers, addition polymers and
condensation polymers.
Addition polymerization happens because of an addition reaction where monomers bond
together without losing any atoms. This happens with monomers that have double bonds,
typically unsaturated carbon molecules. (A saturated compound only has single bonds.)
During the reaction, the double bonds open, allowing the monomers to form a long
continuous chain. The chemical industry uses addition polymerization widely for creating
synthetic polymers, many of which are not biodegradable.
Condensation polymerization occurs when monomers join together but lose some molecules
as by-products. This happens when monomers react that have two functional groups, or a
distinct group of atoms within a molecule. The molecule lost is often water, which will
condense if conditions are right - hence the name.

What Polymers Occur Naturally?

Most of the structures of living things are comprised of natural polymers. There are three
main types. One, polynucleotides, which are chains of nucleotides. Two, polyamides, which
are chains of proteins. And three, polysaccharides, which are chains of sugars.
You probably already know at least one naturally-occurring polymer: DNA, or
deoxyribonucleic acid. You wouldn't be here without it! The DNA molecule is made of
monomers called nucleotides. The monomers are linked by a condensation reaction so that
many nucleotides are linked in a chain to make the DNA polymer molecule, which is why it's
called a polynucleotides.
When you cut your nails or comb your hair, you are dealing with another naturally-occurring
polymer, keratin. Keratin is among the most abundant proteins in humans. Keratin monomers
are amino acids, which form the primary structure of all proteins, a second group of natural
polymers.
Proteins are condensation polymers made from amino acid monomers. One amino acid's
-NH2 functional group reacts with the -COOH functional group of another amino acid,
forming a peptide bond, -CO-NH-. The peptide bond is also called an amide bond, so proteins
are also called polyamides.
Polymer synthesis
Main article: Polymerization

The repeating unit of the polymer polypropylene

Polymerization is the process of combining many small molecules known as monomers into a
covalently bonded chain or network. During the polymerization process, some chemical
groups may be lost from each monomer. This is the case, for example, in the polymerization
of PET polyester. The monomers are terephthalic acid (HOOC-C6H4-COOH) and ethylene
glycol (HO-CH2- CH2-OH) but the repeating unit is -OC-C 6H4-COO-CH2-CH2-O-, which
corresponds to the combination of the two monomers with the loss of two water molecules.
The distinct piece of each monomer that is incorporated into the polymer is known as a repeat
unit or monomer residue.
Laboratory synthetic methods are generally divided into two categories, step-growth
polymerization and chain-growth polymerization.[13] The essential difference between the two
is that in chain growth polymerization, monomers are added to the chain one at a time only,
[14]
such as in polyethylene, whereas in step-growth polymerization chains of monomers may
combine with one another directly,[15] such as in polyester. However, some newer methods
such as plasma polymerization do not fit neatly into either category. Synthetic polymerization
reactions may be carried out with or without a catalyst. Laboratory synthesis of biopolymers,
especially of proteins, is an area of intensive research.

History of Synthetic Polymers

While polymers form the basis of life, the history of synthetic polymers is relatively recent.
Some of the key polymers that have been developed since the early days of polymer science
include:

Vulcanized rubber. In the mid-1800s, American scientist Charles Goodyear began working
with rubber to try to make it more temperature stable. After many unsuccessful attempts, he
accidentally allowed a mixture of sulfur and pre-rubber to touch a hot stove. The rubber did
not melt but only charred a little. By 1844 Goodyear had been given a patent for a process he
called "vulcanization" after the Roman god of fire, Vulcan. Vulcanization is the crosslinking
reaction between the rubber chains and the sulfur.

Bakelite. After years of work in his chemistry lab in Yonkers, New York, Leo Baekeland
announced in 1907 the synthesis of the first truly synthetic polymeric material, later dubbed
"Bakelite." It was generally recognized by leading organic chemists of the nineteenth century
that phenol would condense with formaldehyde, but because they did not understand the
principles of the reaction, they produced useless crosslinked materials. Baekeland's main
project was to make hard objects from phenol and formaldehyde and then dissolve the
product to reform it again in a desired shape. He circumvented the problem by placing the
reactants directly in a mold of the desired shape and then allowing the reactants to form a
hard, clear solidBakelite (Figure 15). It could be worked (i.e., cut, drilled, and sanded), was
resistant to acids and organic liquids, was stable at high temperatures, and did not break down
when exposed to electrical charge. By adding dyes to the starting materials the objects
became available in different colors. Bakelite was used to make bowling balls, phonograph
records, telephone housings, cookware, and billiard balls. Bakelite also acted as a binder for
textiles, sawdust, and paper, forming a wide range of composites including Formica
laminates. Many of these combinations are still in use in the twenty-first century.
Figure 15.

Neoprene. Chemist and Catholic priest Julius A. Nieuwland did extensive work in the 1920s
on acetylene. He found that acetylene could be made to add to itself forming dimers and
trimers. Arnold Collins, a chemist at the Dupont Company in the lab of Wallace Carothers,
continued work on the project and in 1930 ran the reaction described by Nieuwland,
purifying the reaction mixture. He found a small amount of material that was not
vinylacetylene or divinylacetylene. After setting the liquid aside, it solidified into a material
that seemed rubbery and even bounced. This new rubber was given the name Neoprene
(Figure 16). Neoprene has outstanding resistance to gasoline, ozone, and oil in contrast to
natural rubber and is used in a variety of applications including electrical cable jacketing,
window gaskets, shoe soles, industrial hose, and heavy-duty drive belts.

Figure 16.

Nylon. In the early 1930s Wallace Carothers and his team of chemists at Dupont were
investigating synthetic fibers in order to find a synthetic alternative to silk. One promising
candidate was formed from the reaction of adipic acid with hexamethylenediamine and was
called fiber 66 because each monomer-containing unit had six carbons. It formed a strong,
elastic, largely insoluble fiber with a relatively high melting temperature. DuPont chose this
material for production. Such polyamides were given the name "nylons"; thus was born nylon
6,6 (Figure 17).

Figure 17.

Poly(vinyl chloride). While PVC was initially formed by German chemist Eugen Baumann in
1872, scientists at B. F. Goodrich discovered in 1926 how to make sheets and adhesives from
it, starting the "vinyl age." PVC's many applications include water pipes and joints, building
materials, food packaging, wire insulation, and medical components.

Polystyrene. While polystyrene was probably first formed by German apothecary Eduard
Simon in 1839, it was almost 100 years later, in 1930, that the German chemical company I.
G. Fraben placed polystyrene on the market. Polystyrene-molded parts became common
place by 1935. Applications of polystyrene include loose-fill packaging "peanuts," shape-
molded packaging, and disposable utensils.

Polyacrylonitrile. Rohm and Haas Company bought out Plexiglas (polyacrylonitrile [Figure
18]; also known as acrylic and as a fiber sold under tradenames such as Orlon) from a British
firm in 1935 and began production of clear plastic parts and goods, including replacements
for glass in camera lenses, aircraft windows, clock faces, and car tail lights.

Figure 18.

Poly(vinyl butyral). The polymer poly(vinyl butyral) (PVB) was first used in automotive
safety glass in 1938 to prevent flying glass resulting from automobile accidents and continues
to be utilized in the twenty-first century for this purpose (Figure 19).

Figure 19.

Other important synthetic polymers. World War II helped shape the future of polymers.
Wartime demands and shortages encouraged scientists to seek substitutes and materials that
exceeded currently available materials. During and after the war new materials were
developed, spurred by needs in the electronics, medical, communications, food, aerospace,
and other industries. The aromatic nylons (armids) Kevlar (capable of stopping a speeding
bullet and used as tire cord) and Nomex (used in constructing fire-resistant garments) were
developed. Polycarbonates sold under the trade names of Merlon and Lexon were developed
that substituted for glass in many automotive products such as tail lights. Other key
developments included polytetrafluoroethylene, a slick material also known as Teflon;
polysiloxanes, also know as silicones, which have an extremely wide temperature-use range
and were a component of the soles of the shoes that first touched the moon; and polyester
fibers and plastics such as poly(ethylene terephthalate) (PET), used in carbonated
drink bottles (Figure 20).
Figure 20.

Even with this early commercial activity, little was actually known about polymers. German
chemist Herman Staudinger studied the polymerization of isoprene (a five-
carbon hydrocarbon containing a double bond that is obtained as a product of the degradation
of natural rubber by heating) as early as 1910. Intrigued by the difference between this
synthetic material and natural rubber he began to study giant molecules. Many of his fellow
scientists told him there was no such thing as giant molecules and that he was wasting his
time. By 1920 he published a summary of his studies and correctly proposed linear structures
for polystyrene and polyoxymethylene. X-ray studies were used to support the concept of
macromolecules.

Wallace Hume Carothers is considered to be the father of synthetic polymer science. In 1927
the DuPont Company began a program of fundamental research in the areas of colloid
chemistry, catalysis, organic synthesis, and polymer formation. Carothers, then a Harvard
instructor, was persuaded to join the DuPont group. Carothers looked at the construction of
giant molecules from small molecules to form synthetic polymers. His intention was to
prepare molecules of known structure through the use of known organic chemistry and to
"investigate how the properties of these substances depended on constitution." Over the
course of his career, Carothers filed for over fifty patents and was involved in the discovery
of nylon and the synthetic rubber neoprene.

From his studies Carothers established several concepts. First, polymers could be formed by
employing already known organic reactions but with reactants that had more than one
reactive group per molecule. Second, the forces that bring together the individual polymer
units are the same as those that hold together the starting materials: namely, primary covalent
bonds. Much of the polymer chemistry names and ideas that permeate polymer science were
standardized through his efforts.

Types of Synthetic Polymers

Elastomers. Elastomers are polymers possessing chemical and/or physical crosslinks (Table 1
and 2). These crosslinks allow the stretched, deformed segments to return to their original
locations after the force is removed. The "use" temperature must be above the T g to allow
ready chain slippage as the rubbery material is flexed and extended. The forces between the
chains should be minimal to allow easy movement of these chain segments. Finally, the
chains must be present in an amorphous, disorganized fashion. As force is applied and the
material distorts or elongates, the randomly oriented chains are forced to align and take more
ordered positions with the chains, forming crystalline regions that resist ready movement. As
the force is removed the material has a tendency to return to its original disorganized state
and therefore its pre-stretched shape. The formation of the crystalline regions as the material
is stretched gives the material a greater tensile strength(i.e. an increased force is necessary for
further elongation) at high extensions. Crosslinked vinyl polymers are ideal materials to be
used in elastomers: the attractive forces between chains is low and their T g is below room
temperature.

THERMOPLASTIC AND THERMOSETTING

POLYMERS
The response of a polymer to mechanical forces at elevated temperatures is related
to its dominant molecular structure. In fact, one classification scheme for these
materials is according to behavior with rising temperature. Thermoplastics (or
thermoplastic polymers) and thermosets (or thermosetting polymers) are the two
subdivisions. Thermoplastics soften when heated (and eventually liquefy) and
harden when cooledprocesses that are totally reversible and may be repeated.
On a molecular level, as the temperature is raised, secondary bonding forces are
diminished (by increased molecular motion) so that the relative movement of
adjacent chains is facilitated when a stress is applied. Irreversible degradation results
when a molten thermoplastic polymer is raised to too high of a temperature.
In addition, thermoplastics are relatively soft. Most linear polymers and those having
some branched structures with flexible chains are thermoplastic. These materials
are normally fabricated by the simultaneous application of heat and pressure
(see Section 15.22). Most linear polymers are thermoplastics. Examples of common
thermoplastic polymers include polyethylene, polystyrene, poly(ethylene terephthalate),
and poly(vinyl chloride).
Thermosetting polymers are network polymers.They become permanently hard
during their formation, and do not soften upon heating. Network polymers have covalent
crosslinks between adjacent molecular chains. During heat treatments, these
bonds anchor the chains together to resist the vibrational and rotational chain motions
at high temperatures.Thus, the materials do not soften when heated. Crosslinking
is usually extensive, in that 10 to 50% of the chain repeat units are crosslinked.
Only heating to excessive temperatures will cause severance of these crosslink bonds
and polymer degradation. Thermoset polymers are generally harder and stronger
than thermoplastics and have better dimensional stability. Most of the crosslinked
and network polymers, which include vulcanized rubbers, epoxies, and phenolics
and some polyester resins, are thermosetting.

REFERENCE
Strong, A. Brent (2006). "Plastics: Materials and Processing". Pearson Prentice
Hall ISBN 0-13-114558-4

Odian, George (2004). "Priciples of Polymerization" John Wiley & Sons, Inc.

Callister, William D (2014). Material Science and Engineering. Wiley Binder Version
ISBN: 978-1-118-47770-0