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POLYMERS

Polymers are substances whose molecules have high molar masses and are composed of a
large number of repeating units. There are both naturally occurring and synthetic polymers.
Among naturally occurring polymers are proteins, starches, cellulose, and latex. Synthetic
polymers are produced commercially on a very large scale and have a wide range of properties
and uses. The materials commonly called plastics are all synthetic polymers.
Polymers are formed by chemical reactions in which a large number of molecules called
monomers are joined sequentially, forming a chain. In many polymers, only one monomer is
used. In others, two or three different monomers may be combined. Polymers are classified by
the characteristics of the reactions by which they are formed. If all atoms in the monomers are
incorporated into the polymer, the polymer is called an addition polymer. If some of the atoms of
the monomers are released into small molecules, such as water, the polymer is called a
condensation polymer. Most addition polymers are made from monomers containing a double
bond between carbon atoms. Such monomers are called olefins, and most commercial addition
polymers are polyolefins. Condensation polymers are made from monomers that have two
different groups of atoms which can join together to form, for example, ester or amide links.
Polyesters are an important class of commercial polymers, as are polyamides (nylon).

The simplest definition of a polymer is a useful chemical made of many repeating units. A
polymer can be a three dimensional network (think of the repeating units linked together left and
right, front and back, up and down) or two-dimensional network (think of the repeating units
linked together left, right, up, and down in a sheet) or a one-dimensional network (think of the
repeating units linked left and right in a chain). Each repeating unit is the -mer or basic unit
with poly-mer meaning many repeating units. Repeating units are often made of carbon and
hydrogen and sometimes oxygen, nitrogen, sulfur, chlorine, fluorine, phosphorous, and silicon.
To make the chain, many links or -mers are chemically hooked or polymerized together.
Linking countless strips of construction paper together to make paper garlands or hooking
together hundreds of paper clips to form chains, or stringing beads helps visualize
polymers. Polymers occur in nature and can be made to serve specific needs. Manufactured
polymers can be three-dimensional networks that do not melt once formed. Such networks are
called THERMOSET polymers. Epoxy resins used in two-part adhesives are thermoset
plastics. Manufactured polymers can also be one-dimensional chains that can be melted. These
chains are THERMOPLASTIC polymers and are also called LINEAR polymers. Plastic bottles,
films, cups, and fibers are thermoplastic plastics.

Polymers abound in nature. The ultimate natural polymers are the deoxyribonucleic acid (DNA)
and ribonucleic acid (RNA) that define life. Spider silk, hair, and horn are protein
polymers. Starch can be a polymer as is cellulose in wood. Rubber tree latex and cellulose have
been used as raw material to make manufactured polymeric rubber and plastics. The first
synthetic manufactured plastic was Bakelite, created in 1909 for telephone casing and electrical
components. The first manufactured polymeric fiber was Rayon, from cellulose, in 1910. Nylon
was invented in 1935 while pursuing a synthetic spider silk.
The Structure of Polymers
Many common classes of polymers are composed of hydrocarbons, compounds of carbon and
hydrogen. These polymers are specifically made of carbon atoms bonded together, one to the
next, into long chains that are called the backbone of the polymer. Because of the nature of
carbon, one or more other atoms can be attached to each carbon atom in the backbone. There are
polymers that contain only carbon and hydrogen atoms. Polyethylene, polypropylene,
polybutylene, polystyrene and polymethylpentene are examples of these. Polyvinyl chloride
(PVC) has chlorine attached to the all-carbon backbone. Teflon has fluorine attached to the all-
carbon backbone.

Other common manufactured polymers have backbones that include elements other than
carbon. Nylons contain nitrogen atoms in the repeat unit backbone. Polyesters and
polycarbonates contain oxygen in the backbone. There are also some polymers that, instead of
having a carbon backbone, have a silicon or phosphorous backbone. These are considered
inorganic polymers. One of the more famous silicon-based polymers is Silly Putty.

Molecular Arrangement of Polymers


Think of how spaghetti noodles look on a plate. These are similar to how linear polymers can be
arranged if they lack specific order, or are amorphous. Controlling the polymerization process
and quenching molten polymers can result in amorphous organization. An amorphous
arrangement of molecules has no long-range order or form in which the polymer chains arrange
themselves. Amorphous polymers are generally transparent. This is an important characteristic
for many applications such as food wrap, plastic windows, headlight lenses and contact lenses.

Obviously not all polymers are transparent. The polymer chains in objects that are translucent
and opaque may be in a crystalline arrangement. By definition, a crystalline arrangement has
atoms, ions, or in this case, molecules arranged in distinct patterns. You generally think of
crystalline structures in table salt and gemstones, but they can occur in plastics. Just as
quenching can produce amorphous arrangements, processing can control the degree of
crystallinity for those polymers that are able to crystallize. Some polymers are designed to never
be able to crystallize. Others are designed to be able to be crystallized. The higher the degree of
crystallinity, generally, the less light can pass through the polymer. Therefore, the degree of
translucence or opaqueness of the polymer can be directly affected by its
crystallinity. Crystallinity creates benefits in strength, stiffness, chemical resistance, and
stability.

Scientists and engineers are always producing more useful materials by manipulating the
molecular structure that affects the final polymer produced. Manufacturers and processors
introduce various fillers, reinforcements and additives into the base polymers, expanding product
possibilities.

Characteristics of Polymers
The majority of manufactured polymers are thermoplastic, meaning that once the polymer is
formed it can be heated and reformed over and over again. This property allows for easy
processing and facilitates recycling. The other group, the thermosets, cannot be remelted. Once
these polymers are formed, reheating will cause the material to ultimately degrade, but not melt.
Every polymer has very distinct characteristics, but most polymers have the following general
attributes.

1. Polymers can be very resistant to chemicals. Consider all the cleaning fluids in your home that
are packaged in plastic. Reading the warning labels that describe what happens when the
chemical comes in contact with skin or eyes or is ingested will emphasize the need for chemical
resistance in the plastic packaging. While solvents easily dissolve some plastics, other plastics
provide safe, non-breakable packages for aggressive solvents.
2. Polymers can be both thermal and electrical insulators. A walk through your house will
reinforce this concept, as you consider all the appliances, cords, electrical outlets and wiring that
are made or covered with polymeric materials. Thermal resistance is evident in the kitchen with
pot and pan handles made of polymers, the coffee pot handles, the foam core of refrigerators and
freezers, insulated cups, coolers, and microwave cookware. The thermal underwear that many
skiers wear is made of polypropylene and the fiberfill in winter jackets is acrylic and polyester.
3. Generally, polymers are very light in weight with significant degrees of strength. Consider
the range of applications, from toys to the frame structure of space stations, or from delicate
nylon fiber in pantyhose to Kevlar, which is used in bulletproof vests. Some polymers float in
water while others sink. But, compared to the density of stone, concrete, steel, copper, or
aluminum, all plastics are lightweight materials.
4. Polymers can be processed in various ways. Extrusion produces thin fibers or heavy pipes or
films or food bottles. Injection molding can produce very intricate parts or large car body panels.
Plastics can be molded into drums or be mixed with solvents to become adhesives or paints.
Elastomers and some plastics stretch and are very flexible. Some plastics are stretched in
processing to hold their shape, such as soft drink bottles. Other polymers can be foamed like
polystyrene (Styrofoam), polyurethane and polyethylene.
5. Polymers are materials with a seemingly limitless range of characteristics and
colors. Polymers have many inherent properties that can be further enhanced by a wide range of
additives to broaden their uses and applications. Polymers can be made to mimic cotton, silk, and
wool fibers; porcelain and marble; and aluminum and zinc. Polymers can also make possible
products that do not readily come from the natural world, such as clear sheets and flexible films.
6. Polymers are usually made of petroleum, but not always. Many polymers are made of repeat
units derived from natural gas or coal or crude oil. But building block repeat units can
sometimes be made from renewable materials such as polylactic acid from corn or cellulosics
from cotton linters. Some plastics have always been made from renewable materials such as
cellulose acetate used for screwdriver handles and gift ribbon. When the building blocks can be
made more economically from renewable materials than from fossil fuels, either old plastics find
new raw materials or new plastics are introduced.
7. Polymers can be used to make items that have no alternatives from other
materials. Polymers can be made into clear, waterproof films. PVC is used to make medical
tubing and blood bags that extend the shelf life of blood and blood products. PVC safely delivers
flammable oxygen in non-burning flexible tubing. And anti-thrombogenic material, such as
heparin, can be incorporated into flexible PVC catheters for open heart surgery, dialysis, and
blood collection. Many medical devices rely on polymers to permit effective functioning.
Classifications of Polymers

Thermoplastics

Molecules in a thermoplastic are held together by relatively weak intermolecular forces so that
the material softens when exposed to heat and then returns to its original condition when cooled.
Thermoplastic polymers can be repeatedly softened by heating and then solidified by cooling - a
process similar to the repeated melting and cooling of metals. Most linear and slightly branched
polymers are thermoplastic. All the major thermoplastics are produced by chain polymerization,

Thermoplastics have a wide range of applications because they can be formed and reformed in so
many shapes. Some examples are food packaging, insulation, automobile bumpers, and credit
cards.

Thermosets

A thermosetting plastic, or thermoset, solidifies or "sets"


irreversibly when heated. Thermosets cannot be reshaped
by heating. Thermosets usually are three-
dimensional networked polymers in which there is a high
degree of cross-linking between polymer chains. The
cross-linking restricts the motion of the chains and leads to
a rigid material.

A simulated skeletal structure of a network polymer with a


high cross-link density is shown at the right.

Thermosets are strong and durable. They primarily are


used in automobiles and construction. They also are used
to make toys, varnishes, boat hulls, and glues.
Elastomers

Elastomers are rubbery polymers that can be stretched


easily to several times their un-stretched length and which
rapidly return to their original dimensions when the
applied stress is released.

Elastomers are cross-linked, but have a low cross-link


density. The polymer chains still have some freedom to
move, but are prevented from permanently moving
relative to each other by the cross-links.

To stretch, the polymer chains must not be part of a rigid


solid - either a glass or a crystal. An elastomer must be
above its glass transition temperature, and have a low
degree of crystallinity.

Rubber bands and other elastics are made of elastomers.

Crystalline Polymers

Highly crystalline polymers are rigid, high melting, and less affected by solvent penetration.
Crystallinity makes a polymers strong, but also lowers their impact resistance. As an example,
samples of polyethylene prepared under high pressure (5000 atm) have high crystallinities (95 -
99%) but are extremely brittle21.

Small molecules and ions form a


three-dimensional lattice with an
extended regular structure that
makes large crystals possible. A
small portion of the NaCl lattice is
modeled in the diagram at the right.

We usually describe such lattices


with a unit cell - the smallest
repeating unit in the lattice . In the
case of NaCl, the unit cell is said to
be face-centered cubic.
Polymer molecules
are very large so it might
seem that they could not
pack together regularly and
form a crystal. It now is
known that regular
polymers may
form lamellar (plate-like)
crystals with a thickness of
10 to 20 nm in which the
parallel chains (shown in
different colors in the
simulated structure at the
right) are perpendicular to
the face of the crystals18.

Amorphous Polymers

Polymer chains with branches or irregular pendant groups


cannot pack together regularly enough to form crystals.
These polymers are said to be amorphous. A two-
dimensional schematic of an amorphous polymer is shown
at the right.

Amorphous regions of a polymer are made up of a


randomly coiled and entangled chains. They have been
compared to a bucket containing a large number of
entangled worms - each one 20-feet long and of 1/4-inch
thickness1. The worms are so tangled that an entire worm
cannot slide past the others, but small portions of the
worms can twist around within the mass.

Amorphous polymers are softer, have lower melting


points, and are penetrated more by solvents than are their
crystalline counterparts.

Glassy and Rubber States

At low temperatures molecular motion in an amorphous region is restricted to molecular


vibrations, but the chains cannot rotate or move in space (the worms are frozen and cannot
move). This form is the glassy state of the amorphous region. The glassy state can be thought of
as being a super cooled liquid where the molecular motions have been frozen in. The glassy state
is hard, rigid, and brittle like a crystalline solid, but retains the molecular disorder of a liquid33.
When the material is heated the polymer will reach a temperature at which segments (20 - 50
atoms long) of the entangled chains can move (small portions of the entangled worms can move
around so the mass in the bucket writhes). At this temperature, called the glass transition
temperature, the amorphous region becomes rubbery. When an amorphous polymer is in its
rubbery state it is soft and flexible.

Semi-Crystalline Polymers

Semi-crystalline polymers have both crystalline and amorphous regions. Semi-crystallinity is a


desirable property for most plastics because they combine the strength of crystalline polymers
with the flexibility of amorphous. Semi-crystalline polymers can be tough with an ability to bend
without breaking,

Isolated lamellar single crystals are obtained by


crystallization from dilute solution. When crystals are
formed from the melt, chain entanglements are
extremely important19. In this case the solid is more
irregular with polymer chains meandering in and out
of ordered crystalline portions. The crystalline
portion is in the lamellae; the amorphous portion is
outside the lamallae24.

Polymers such as this are said to be semi-crystalline.


The crystals are small and connected to the
amorphous regions by polymer chains so there may
be no sharp well-defined boundaries between the two
types of regions. For some polymers, such
as polyvinyl alcohol, there is a fairly distinct
separation between the crystalline and amorphous
regions, though. In other cases the structure basically
is crystalline with uniformly-distributed flaws and
imperfections20.

If we model a polymer as having distinct crystalline and amorphous regions then the percentage
of the polymer that is crystalline is called the percent crystallinity. The percent crystallinity has
an important influence on the properties of the polymer.
Spherulites

When a molten crystallizable polymer cools, the


crystals grow from individual nuclei and radiate out
like the spokes of a bicycle wheel as is illustrated in
the schematic diagram at the right. The crystalline
portions actually radiate out in in three dimensions,
forming spheres that are called spherulites. In a
sample of a crystalline polymer there are billions of
spherulites.

Over the past few decades, the use of polymers in disposable consumer goods has grown
tremendously. This growth is proving to be taxing on the waste disposal system, consuming a
large fraction of available landfill space. Furthermore, the raw materials for these polymers are
obtained from petroleum, a limited, non-renewable resource. To reduce the demand for landfill
space and the consumption of limited petroleum reserves, the recycling of polymers has become
a subject of concern. One of the problems faced in recycling polymers is the great variety of
polymers in use. To help sort wastes by type of polymer, most disposable polymeric goods are
labeled with a recycling code: three arrows around a number above the polymer's acronym.
These are intended to help consumers separate the waste polymers according to type before
disposing of them. (In the city of Madison, currently only type 1 (PETE) and type 2 (HDPE)
polymers are being recycled see below. These account for over 90% of all waste plastic
containers. Other plastics comprise less than 1% of household waste.) The recycling of polymers
is not a closed loop, where a material is reformed into new products repeatedly, such as is the
case with aluminum. Most polymeric materials are recycled only once, and the product made of
recycled polymer is discarded after use. To obtain the maximum benefit from recycled polymer,
the products made from it generally are intended to have a relatively long useful life. Recycled
polymers are used in such products as cafeteria trays, large plastic toys, impact absorbing
highway pylons, and carpeting. Some recycled PETE is now used in 2-liter soft-drink containers.
In general, products made from recycled polymers are more expensive than those made from
virgin plastic. This is the case because current manufacturing facilities are geared to production
from new materials. As more factories capable of using recycled plastics are constructed, the
costs of using recycled polymers will decline. More such factories will be built soon only if we
are willing to pay up front the costs of recycling (as higher prices of consumer goods), rather
than delaying costs of disposal (in the form of increased taxes).
Solid Waste Management
In addressing all the superior attributes of polymers, it is equally important to discuss some of
the challenges associated with the materials. Most plastics deteriorate in full sunlight, but never
decompose completely when buried in landfills. However, other materials such as glass, paper,
or aluminum do not readily decompose in landfills either. Some bioplastics do decompose to
carbon dioxide and water, however, in specially designed food waste commercial composting
facilities ONLY. They do not biodegrade under other circumstances.

For 20051 the EPA characterization of municipal solid waste before recycling for the United
States showed plastics made up 11.8 percent of our trash by weight compared to paper that
constituted 34.2 percent. Glass and metals made up 12.8 percent by weight. And yard trimmings
constituted 13.1 percent of municipal solid waste by weight. Food waste made up 11.9 percent of
municipal solid waste. The characteristics that make polymers so attractive and useful,
lightweight and almost limitless physical forms of many polymers designed to deliver specific
appearance and functionality, make post-consumer recycling challenging. When enough used
plastic items can be gathered together, companies develop technology to recycle those used
plastics. The recycling rate for all plastics is not as high as any would want. But, the recycling
rate for the 1,170,000,000 pounds of polyester bottles, 23.1%, recycled in 2005 and the
953,000,000 pounds of high density polyethylene bottles, 28.8%, recycled in 2005 show that
when critical mass of defined material is available, recycling can be a commercial success2.
Applications for recycled plastics are growing every day. Recycled plastics can be blended with
virgin plastic (plastic that has not been processed before) without sacrificing properties in many
applications. Recycled plastics are used to make polymeric timbers for use in picnic tables,
fences and outdoor playgrounds, thus providing low maintenance, no splinters products and
saving natural lumber. Plastic from soft drink and water bottles can be spun into fiber for the
production of carpet or made into new food bottles. Closed loop recycling does occur, but
sometimes the most valuable use for a recycled plastic is into an application different than the
original use.

An option for plastics that are not recycled, especially those that are soiled, such as used food
wrap or diapers, can be a waste-to-energy system (WTE). In 2005, 13.6% of US municipal solid
waste was processed in WTE systems1. When localities decide to use waste-to-energy systems to
manage solid waste, plastics can be a useful component.
The controlled combustion of polymers produces heat energy. The heat energy produced by the
burning plastic municipal waste not only can be converted to electrical energy but also helps
burn the wet trash that is present. Paper also produces heat when burned, but not as much as do
plastics. On the other hand, glass, aluminum and other metals do not release any energy when
burned.

To better understand the incineration process, consider the smoke coming off a burning item. If
one were to ignite the smoke with a lit propane torch, one would observe that the smoke
disappears. This exercise illustrates that the by-products of incomplete burning are still
flammable. Proper incineration burns the material and the by-products of the initial burning and
also takes care of air and solid emissions to insure public safety.

Some plastics can be composted either because of special additives or because of the
construction of the polymers. Compostable plastics frequently require more intense conditions
to decompose than are available in backyard compost piles. Commercial composters are
suggested for compostable plastics. In 20051, composting processed 8.4% of US municipal solid
waste.

Plastics can also be safely land filled, although the valuable energy resource of the plastics would
then be lost for recycling or energy capture. In 20051, 54.3% of US municipal solid waste was
land filled. Plastics are used to line landfills so that leachate is captured and groundwater is not
polluted. Non-degrading plastics help stabilize the ground so that after the landfill is closed, the
land can be stable enough for useful futures.

Polymers affect every day of our life. These materials have so many varied characteristics and
applications that their usefulness can only be measured by our imagination. Polymers are the
materials of past, present and future generations.