Polymer

Appearance of real linear polymer chains as recorded using an atomic force microscope on surface under liquid medium.
Chain contour length for this polymer is ~204 nm; thickness is ~0.4 nm.[1]

A polymer is a large molecule (macromolecule) composed of repeating structural units typically connected

by covalent chemical bonds. Whilepolymer in popular usage suggests plastic, the term actually refers to a large
class of natural and synthetic materials with a wide variety of properties.

Because of the extraordinary range of properties accessible in polymeric materials, [2] they play an essential and
ubiquitous role in everyday life[3], ranging from familiar synthetic plastics and elastomers to natural biopolymers
such as DNA and proteins that are essential for life. A simple example is polyethylene, whose repeating unit is
based on ethylene (IUPAC name ethene) monomer. Most commonly, as in this example, the continuously
linked backbone of a polymer used for the preparation of plastics consists mainly of carbon atoms. However,
other structures do exist; for example, elements such as silicon form familiar materials such as silicones,
examples being silly putty and waterproof plumbing sealant. The backbone of DNAis in fact based on
a phosphodiester bond, and repeating units of polysaccharides (e.g. cellulose) are joined together by glycosidic
bonds via oxygen atoms.

Natural polymeric materials such as shellac, amber, and natural rubber have been in use for
centuries. Biopolymers such as proteins and nucleic acids play crucial roles in biological processes. A variety of
other natural polymers exist, such as cellulose, which is the main constituent of wood and paper.

The list of synthetic polymers includes synthetic

rubber, Bakelite, neoprene, nylon, PVC, polystyrene, polyethylene, polypropylene, polyacrylonitrile,PVB, silicon
e, and many more.

Polymers are studied in the fields of polymer chemistry, polymer physics, and polymer science.
Etymology
The word polymer is derived from the Greek words πολυ- - poly- meaning "many"; and μέρος -
meros meaning "part". The term was coined in 1833 by Jöns Jacob Berzelius, although his definition of a
polymer was quite different from the modern definition. (see New chemical terms)

[edit]Historical development
Starting in 1811, Henri Braconnot did pioneering work in derivative cellulose compounds, perhaps the
earliest important work in polymer science. The development of vulcanization later in the nineteenth
century improved the durability of the natural polymer rubber, signifying the first popularized semi-
synthetic polymer. In 1907, Leo Baekeland created the first completely synthetic polymer, Bakelite, by
reacting phenol and formaldehyde at precisely controlled temperature and pressure. Bakelite was then
publicly introduced in 1909.

Despite significant advances in synthesis and characterization of polymers, a correct understanding of

polymer molecular structure did not emerge until the 1920s. Before then, scientists believed that polymers
were clusters of small molecules (called colloids), without definite molecular weights, held together by an
unknown force, a concept known as association theory. In 1922, Hermann Staudinger proposed that
polymers consisted of long chains of atoms held together by covalent bonds, an idea which did not gain
wide acceptance for over a decade and for which Staudinger was ultimately awarded the Nobel Prize.
Work by Wallace Carothers in the 1920s also demonstrated that polymers could be synthesized rationally
from their constituent monomers. An important contribution to synthetic polymer science was made by the
Italian chemist Giulio Natta and the German chemist Karl Ziegler, who won the Nobel Prize in Chemistry
in 1963 for the development of the Ziegler-Natta catalyst. Further recognition of the importance of
polymers came with the award of the Nobel Prize in Chemistry in 1974 to Paul Flory, whose extensive
work on polymers included the kinetics of step-growth polymerization and of addition
polymerization, chain transfer, excluded volume, the Flory-Huggins solution theory, and the Flory
convention.

Synthetic polymer materials such as nylon, polyethylene, Teflon, and silicone have formed the basis for a
burgeoning polymer industry. These years have also shown significant developments in rational polymer
synthesis. Most commercially important polymers today are entirely synthetic and produced in high
volume on appropriately scaled organic synthetic techniques. Synthetic polymers today find application in
nearly every industry and area of life. Polymers are widely used as adhesives and lubricants, as well as
structural components for products ranging from children's toys to aircraft. They have been employed in a
variety of biomedical applications ranging from implantable devices to controlled drug delivery. Polymers
such as poly(methyl methacrylate) find application as photoresist materials used
in semiconductor manufacturing and low-k dielectrics for use in high-performance microprocessors.
Recently, polymers have also been employed as flexible substrates in the development of organic light-
emitting diodes for electronic display.

[edit]Polymer synthesis
Main article:  Polymerization

The repeating unit of the polymerpolypropylene

Polymerization is the process of combining many small molecules known as monomers into a covalently

bonded chain. 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-C6H4-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.

[edit]Laboratory synthesis
Laboratory synthetic methods are generally divided into two categories, step-growth
polymerization and chain-growth polymerization[4]. The essential difference between the two is that in
chain growth polymerization, monomers are added to the chain one at a time only [5], whereas in step-
growth polymerization chains of monomers may combine with one another directly [6]. 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.

[edit]Biological synthesis
Main article:  Biopolymer

There are three main classes of biopolymers: polysaccharides, polypeptides, and polynucleotides. In

living cells, they may be synthesized by enzyme-mediated processes, such as the formation
of DNA catalyzed by DNA polymerase. The synthesis of proteins involves multiple enzyme-mediated
processes to transcribe genetic information from the DNA to RNA and subsequently translate that
information to synthesize the specified protein from amino acids. The protein may be modified
further following translation in order to provide appropriate structure and functioning.

[edit]Modification of natural polymers

Many commercially important polymers are synthesized by chemical modification of naturally occurring
polymers. Prominent examples include the reaction of nitric acid and cellulose to form nitrocellulose and
the formation of vulcanized rubber by heating natural rubber in the presence of sulfur.

[edit]Polymer properties
Polymer properties are broadly divided into several classes based on the scale at which the property is
defined as well as upon its physical basis[7]. The most basic property of a polymer is the identity of its
constituent monomers. A second set of properties, known as microstructure, essentially describe the
arrangement of these monomers within the polymer at the scale of a single chain. These basic structural
properties play a major role in determining bulk physical properties of the polymer, which describe how
the polymer behaves as a continuous macroscopic material. Chemical properties, at the nano-scale,
describe how the chains interact through various physical forces. At the macro-scale, they describe how
the bulk polymer interacts with other chemicals and solvents.

[edit]Monomers and repeat units

The identity of the monomer residues (repeat units) comprising a polymer is its first and most important
attribute. Polymer nomenclature is generally based upon the type of monomer residues comprising the
polymer. Polymers that contain only a single type of repeat unit are known as homopolymers, while
polymers containing a mixture of repeat units are known ascopolymers. Poly(styrene), for example, is
composed only of styrene monomer residues, and is therefore classified as a homopolymer. Ethylene-
vinyl acetate, on the other hand, contains more than one variety of repeat unit and is thus a copolymer.
Some biological polymers are composed of a variety of different but structurally related monomer
residues; for example, polynucleotides such as DNA are composed of a variety of nucleotide subunits.

A polymer molecule containing ionizable subunits is known as a polyelectrolyte or ionomer.

[edit]Microstructure

The microstructure of a polymer (sometimes called configuration) relates to the physical arrangement of
monomer residues along the backbone of the chain[8]. These are the elements of polymer structure that
require the breaking of a covalent bond in order to change. Structure has a strong influence on the other
properties of a polymer. For example, two samples of natural rubber may exhibit different durability, even
though their molecules comprise the same monomers.
[edit]Polymer architecture

Branch point in a polymer

An important microstructural feature determining polymer properties is the polymer architecture. [9] The
simplest polymer architecture is a linearchain: a single backbone with no branches. A related unbranching
architecture is a ring polymer. A branched polymer molecule is composed of a main chain with one or
more substituent side chains or branches. Special types of branched polymers include star
polymers, comb polymers,brush polymers, dendronized polymers, ladders, and dendrimers[9].

Branching of polymer chains affects the ability of chains to slide past one another by altering
intermolecular forces, in turn affecting bulk physical polymer properties. Long chain branches may
increase polymer strength, toughness, and the glass transition temperature (Tg) due to an increase in the
number of entanglements per chain. The effect of such long-chain branches on the size of the polymer in
solution is characterized by the branching index. Random length and atactic short chains, on the other
hand, may reduce polymer strength due to disruption of organization and may likewise reduce the
crystallinity of the polymer.

A good example of this effect is related to the range of physical attributes of polyethylene. High-density
polyethylene (HDPE) has a very low degree of branching, is quite stiff, and is used in applications such as
milk jugs. Low-density polyethylene (LDPE), on the other hand, has significant numbers of both long and
short branches, is quite flexible, and is used in applications such as plastic films.

Dendrimer and dendron

Dendrimers are a special case of polymer where every monomer unit is branched. This tends to reduce
intermolecular chain entanglement and crystallization. Alternatively, dendritic polymers are not perfectly
branched but share similar properties to dendrimers due to their high degree of branching.

The architecture of the polymer is often physically determined by the functionality of the monomers from
which it is formed[10]. This property of a monomer is defined as the number of reaction sites at which may
form chemical covalent bonds. The basic functionality required for forming even a linear chain is two
bonding sites. Higher functionality yields branched or even crosslinked or networked polymer chains.

An effect related to branching is chemical crosslinking - the formation of covalent bonds between chains.
Crosslinking tends to increase Tg and increase strength and toughness. Among other applications, this
process is used to strengthen rubbers in a process known as vulcanization, which is based on
crosslinking by sulfur. Car tires, for example, are highly crosslinked in order to reduce the leaking of air
out of the tire and to toughen their durability. Eraser rubber, on the other hand, is not crosslinked to allow
flaking of the rubber and prevent damage to the paper.

A cross-link suggests a branch point from which four or more distinct chains emanate. A polymer
molecule with a high degree of crosslinking is referred to as a polymer network. [11]Sufficiently high
crosslink concentrations may lead to the formation of an infinite network, also known as a gel, in which
networks of chains are of unlimited extent—essentially all chains have linked into one molecule. [12]
[edit]Chain length

The physical properties[13] of a polymer are strongly dependent on the size or length of the polymer chain.
[14]
. For example, as chain length is increased, melting and boiling temperatures increase quickly [14].
Impact resistance also tends to increase with chain length, as does the viscosity, or resistance to flow, of
the polymer in its melt state[15]. Chain length is related to melt viscosity roughly as 1:10 3.2, so that a tenfold
increase in polymer chain length results in a viscosity increase of over 1000 times [citation needed]. Increasing
chain length furthermore tends to decrease chain mobility, increase strength and toughness, and increase
the glass transition temperature (Tg)[citation needed]. This is a result of the increase in chain interactions such
as Van der Waals attractions and entanglements that come with increased chain length [citation needed]. These
interactions tend to fix the individual chains more strongly in position and resist deformations and matrix
breakup, both at higher stresses and higher temperatures [citation needed].

A common means of expressing the length of a chain is the degree of polymerization, which quantifies the
number of monomers incorporated into the chain[16][17]. As with other molecules, a polymer's size may also
be expressed in terms of molecular weight. Since synthetic polymerization techniques typically yield a
polymer product including a range of molecular weights, the weight is often expressed statistically to
describe the distribution of chain lengths present in the same. Common examples are the number
average molecular weight and weight average molecular weight[18][19]. The ratio of these two values is
the polydispersity index, commonly used to express the "width" of the molecular weight distribution. [20] A
final measurement is contour length, which can be understood as the length of the chain backbone in its
fully extended state[21].

The flexibility of an unbranched chain polymer is characterized by its persistence length.

[edit]Monomer arrangement in copolymers
Main article:  copolymer

Monomers within a copolymer may be organized along the backbone in a variety of ways.

 Alternating copolymers possess regularly alternating monomer residues:[22] [AB...]n (2).

 Periodic copolymers have monomer residue types arranged in a repeating sequence: [A nBm...]
m being different from n .
 Statistical copolymers have monomer residues arranged according to a known statistical rule. A
statistical copolymer in which the probability of finding a particular type of monomer residue at an
particular point in the chain is independent of the types of surrounding monomer residue may be
referred to as a truly random copolymer[23][24] (3).
 Block copolymers have two or more homopolymer subunits linked by covalent bonds [22] (4).
Polymers with two or three blocks of two distinct chemical species (e.g., A and B) are called diblock
copolymers and triblock copolymers, respectively. Polymers with three blocks, each of a different
chemical species (e.g., A, B, and C) are termed triblock terpolymers.
 Graft or grafted copolymers contain side chains that have a different composition or
configuration than the main chain.(5)
[edit]Tacticity
Main article:  Tacticity
Tacticity describes the relative stereochemistry of chiral centers in neighboring structural units within a
macromolecule. There are three types: isotactic (all substituents on the same side), atactic (random
placement of substituents), and syndiotactic (alternating placement of substituents).

[edit]Polymer morphology
Polymer morphology generally describes the arrangement of chains in space and microscopic ordering of
many polymer chains.
[edit]Crystallinity

When applied to polymers, the term crystalline has a somewhat ambiguous usage. In some cases, the
term crystalline finds identical usage to that used in conventional crystallography. For example, the
structure of a crystalline protein or polynucleotide, such as a sample prepared for x-ray crystallography,
may be defined in terms of a conventional unit cell composed of one or more polymer molecules with cell
dimensions of hundreds of angstroms or more.

A synthetic polymer may be lightly described as crystalline if it contains regions of three-dimensional

ordering on atomic (rather than macromolecular) length scales, usually arising from intramolecular folding
and/or stacking of adjacent chains. Synthetic polymers may consist of both crystalline and amorphous
regions; the degree of crystallinity may be expressed in terms of a weight fraction or volume fraction of
crystalline material. Few synthetic polymers are entirely crystalline. [25]

The crystallinity of polymers is characterized by their degree of crystallinity, ranging from zero for a
completely non-crystalline polymer to one for a theoretical completely crystalline polymer. Polymers with
microcrystalline regions are generally tougher (can be bent more without breaking) and more impact-
resistant than totally amorphous polymers.[26]

Polymers with a degree of crystallinity approaching zero or one will tend to be transparent, while polymers
with intermediate degrees of crystallinity will tend to be opaque due to light scattering by crystalline or
glassy regions. Thus for many polymers, reduced crystallinity may also be associated with increased
transparency.
[edit]Chain conformation

The space occupied by a polymer molecule is generally expressed in terms of radius of gyration, which is
an average distance from the center of mass of the chain to the chain itself. Alternatively, it may be
expressed in terms of pervaded volume, which is the volume of solution spanned by the polymer chain
and scales with the cube of the radius of gyration.[27]

[edit]Mechanical properties
The bulk properties of a polymer are those most often of end-use interest. These are the properties that
indictate how the polymer actually behaves on a macroscopic scale.
[edit]Tensile strength

The tensile strength of a material quantifies how much stress the material will endure before suffering
permanent deformation.[28][29] This is very important in applications that rely upon a polymer's physical
strength or durability. For example, a rubber band with a higher tensile strength will hold a greater weight
before snapping. In general, tensile strength increases with polymer chain length and crosslinking of
polymer chains.
[edit]Young's modulus of elasticity

Young's Modulus quantifies the elasticity of the polymer. It is defined, for small strains, as the ratio of rate
of change of stress to strain. Like tensile strength, this is highly relevant in polymer applications involving
the physical properties of polymers, such as rubber bands. The modulus is strongly dependent on
temperature.
[edit]Transport properties

Transport properties such as diffusivity relate to how rapidly molecules move through the polymer matrix.
These are very important in many applications of polymers for films and membranes.

[edit]Phase behavior
[edit]Melting point

The term melting point, when applied to polymers, suggests not a solid-liquid phase transition but a
transition from a crystalline or semi-crystalline phase to a solid amorphous phase. Though abbreviated as
simply Tm, the property in question is more properly called the crystalline melting temperature. Among
synthetic polymers, crystalline melting is only discussed with regards to thermoplastics,
as thermosetting polymers will decompose at high temperatures rather than melt.
[edit]Boiling point

The boiling point of a polymeric material is strongly dependent on chain length. High polymers with a
large degree of polymerization do not exhibit a boiling point because they decompose before reaching
theoretical boiling temperatures. For shorter oligomers, a boiling transition may be observed and will
generally increase rapidly as chain length is increased.
[edit]Glass transition temperature

A parameter of particular interest in synthetic polymer manufacturing is the glass transition

temperature (Tg), which describes the temperature at which amorphous polymers undergo a second-order
phase transition from a rubbery, viscous amorphous solid, or from a crystalline solid (depending on the
degree of crystallization) to a brittle, glassy amorphous solid. The glass transition temperature may be
engineered by altering the degree of branching or crosslinking in the polymer or by the addition
of plasticizer.[30]
[edit]Mixing behavior

Phase diagram of the typical mixing behavior of weakly interacting polymer solutions.

In general, polymeric mixtures are far less miscible than mixtures of small molecule materials. This effect
results from the fact that the driving force for mixing is usually entropy, not interaction energy. In other
words, miscible materials usually form a solution not because their interaction with each other is more
favorable than their self-interaction, but because of an increase in entropy and hence free energy
associated with increasing the amount of volume available to each component. This increase in entropy
scales with the number of particles (or moles) being mixed. Since polymeric molecules are much larger
and hence generally have much higher specific volumes than small molecules, the number of molecules
involved in a polymeric mixture is far smaller than the number in a small molecule mixture of equal
volume. The energetics of mixing, on the other hand, is comparable on a per volume basis for polymeric
and small molecule mixtures. This tends to increase the free energy of mixing for polymer solutions and
thus make solvation less favorable. Thus, concentrated solutions of polymers are far rarer than those of
small molecules.

Furthermore, the phase behavior of polymer solutions and mixtures is more complex than that of small
molecule mixtures. Whereas most small molecule solutions exhibit only an upper critical solution
temperature phase transition, at which phase separation occurs with cooling, polymer mixtures commonly
exhibit a lower critical solution temperaturephase transition, at which phase separation occurs with
heating.

In dilute solution, the properties of the polymer are characterized by the interaction between the solvent
and the polymer. In a good solvent, the polymer appears swollen and occupies a large volume. In this
scenario, intermolecular forces between the solvent and monomer subunits dominate over intramolecular
interactions. In a bad solvent or poor solvent, intramolecular forces dominate and the chain contracts. In
the theta solvent, or the state of the polymer solution where the value of the second virial coefficient
becomes 0, the intermolecular polymer-solvent repulsion balances exactly the intramolecular monomer-
monomer attraction. Under the theta condition (also called the Flory condition), the polymer behaves like
an ideal random coil.
[edit]Inclusion of plasticizers

Inclusion of plasticizers tends to lower Tg and increase polymer flexibility. Plasticizers are generally small

molecules that are chemically similar to the polymer and create gaps between polymer chains for greater
mobility and reduced interchain interactions. A good example of the action of plasticizers is related to
polyvinylchlorides or PVCs. A uPVC, or unplasticized polyvinylchloride, is used for things such as pipes. A
pipe has no plasticizers in it, because it needs to remain strong and heat-resistant. Plasticized PVC is
used for clothing for a flexible quality. Plasticizers are also put in some types of cling film to make the
polymer more flexible.

[edit]Chemical properties
The attractive forces between polymer chains play a large part in determining a polymer's properties.
Because polymer chains are so long, these interchain forces are amplified far beyond the attractions
between conventional molecules. Different side groups on the polymer can lend the polymer to ionic
bonding or hydrogen bonding between its own chains. These stronger forces typically result in higher
tensile strength and higher crystalline melting points.

The intermolecular forces in polymers can be affected by dipoles in the monomer units. Polymers
containing amide or carbonyl groups can form hydrogen bonds between adjacent chains; the partially
positively charged hydrogen atoms in N-H groups of one chain are strongly attracted to the partially
negatively charged oxygen atoms in C=O groups on another. These strong hydrogen bonds, for example,
result in the high tensile strength and melting point of polymers
containing urethane or urea linkages. Polyesters have dipole-dipole bondingbetween the oxygen atoms in
C=O groups and the hydrogen atoms in H-C groups. Dipole bonding is not as strong as hydrogen
bonding, so a polyester's melting point and strength are lower than Kevlar's (Twaron), but polyesters have
greater flexibility.
Ethene, however, has no permanent dipole. The attractive forces between polyethylene chains arise from
weak van der Waals forces. Molecules can be thought of as being surrounded by a cloud of negative
electrons. As two polymer chains approach, their electron clouds repel one another. This has the effect of
lowering the electron density on one side of a polymer chain, creating a slight positive dipole on this side.
This charge is enough to attract the second polymer chain. Van der Waals forces are quite weak,
however, so polyethylene can have a lower melting temperature compared to other polymers.

[edit]Standardized polymer nomenclature

There are multiple conventions for naming polymer substances. Many commonly used polymers, such as
those found in consumer products, are referred to by a common or trivial name. The trivial name is
assigned based on historical precedent or popular usage rather than a standardized naming convention.
Both the American Chemical Society[31] and IUPAC[32] have proposed standardized naming conventions;
the ACS and IUPAC conventions are similar but not identical. [33] Examples of the differences between the
various naming conventions are given in the table below:

Common name ACS name IUPAC name

Poly(ethylene oxide) or PEO Poly(oxyethylene) Poly(oxyethene)

Poly(ethylene Poly(oxy-1,2-ethanediyloxycarbonyl-1,4-
Poly(oxyetheneoxyterephthaloyl)
terephthalate) or PET phenylenecarbonyl)

Nylon 6 Poly[amino(1-oxo-1,6-hexanediyl)] Poly[amino(1-oxohexan-1,6-diyl)]

In both standardized conventions, the polymers' names are intended to reflect the monomer(s) from
which they are synthesized rather than the precise nature of the repeating subunit. For example, the
polymer synthesized from the simple alkene ethene is called polyethylene, retaining the -ene suffix even
though the double bond is removed during the polymerization process:
[edit]Polymer characterization
The characterization of a polymer requires several parameters which need to be specified. This is
because a polymer actually consists of a statistical distribution of chains of varying lengths, and each
chain consists of monomer residues which affect its properties.

A variety of lab techniques are used to determine the properties of polymers. Techniques such as wide
angle X-ray scattering, small angle X-ray scattering, and small angle neutron scattering are used to
determine the crystalline structure of polymers. Gel permeation chromatography is used to determine
the number average molecular weight, weight average molecular weight,
and polydispersity. FTIR, Raman and NMR can be used to determine composition. Thermal properties
such as the glass transition temperature and melting point can be determined by differential scanning
calorimetry and dynamic mechanical analysis. Pyrolysis followed by analysis of the fragments is one
more technique for determining the possible structure of the polymer. Thermogravimetry is a useful
technique to evaluate the thermal stability of the polymer. Detailed analyses of TG curves also allow us to
know a bit of the phase segregation in polymers. Rheological properties are also commonly used to help
determine molecular architecture (molecular weight, molecular weight distribution and branching)as well
as to understand how the polymer will process, through measurements of the polymer in the melt phase.
Another Polymer characterization technique is Automatic Continuous Online Monitoring of Polymerization
Reactions (ACOMP) which provides real-time characterization of polymerization reactions. It can be used
as an analytical method in R&D, as a tool for reaction optimization at the bench and pilot plant level and,
eventually, for feedback control of full-scale reactors. ACOMP measures in a model-independent fashion
the evolution of average molar mass and intrinsic viscosity, monomer conversion kinetics and, in the case
of copolymers, also the average composition drift and distribution. It is applicable in the areas of free
radical and controlled radical homo- and copolymerization, polyelectrolyte synthesis, heterogeneous
phase reactions, including emulsion polymerization, adaptation to batch and continuous reactors, and
modifications of polymers.[34][35][36]
[edit]Polymer degradation

A plastic item with thirty years of exposure to heat and cold, brake fluid, and sunlight. Notice the discoloration, swollen
dimensions, and tiny splits running through the material

Polymer degradation is a change in the properties—tensile strength, color, shape, molecular weight, etc.
—of a polymer or polymer-based product under the influence of one or more environmental factors, such
as heat, light, chemicals and, in some cases, galvanic action. It is often due to the hydrolysis of the bonds
connecting the polymer chain, which in turn leads to a decrease in the molecular mass of the polymer.
These changes may be undesirable, such as changes during use, or desirable, as in biodegradation or
deliberately lowering the molecular mass of a polymer. Such changes occur primarily because of the
effect of these factors on the chemical composition of the polymer. Ozone cracking and UV
degradation are specific failure modes for certain polymers. The susceptibility of a polymer to degradation
depends on its structure. Epoxies and chains containing aromatic functionality are especially susceptible
to UV degradationwhile polyesters are susceptible to degradation by hydrolysis. Carbon based polymers
are more susceptible to thermal degradation than inorganically bound polymers such
as Polydimethylsiloxane and are therefore not ideal for most high temperature applications.

Polymer degradation may occur through galvanic action similar to that of metals. In 1990, Michael
Faudree discovered that imide-linked resins in CFRP (carbon fiber reinforced
polymers) composites degrade when bare composite is coupled with an active metal in saline, i.e. salt
water environments.[37][38]Polymers affected include bismaleimides (BMI),
condensation polyimides, triazines, and blends thereof. Degradation occurs in the form of dissolved resin
and loose fibers. Hydroxyl ions are generated at the graphite cathode attacking the O-C-N bond in the
polyimide structure. This phenomenon, that polymers can undergo galvanic corrosion like metals do has
been referred to as the "Faudree Effect". Standard corrosion protection procedures were found to prevent
polymer degradation under most conditions.
The degradation of polymers to form smaller molecules may proceed by random scission or specific
scission. The degradation of polyethylene occurs by random scission—a random breakage of the
linkages (bonds) that hold the atoms of the polymer together. When heated above 450 DEGC it degrades
to form a mixture of hydrocarbons. Other polymers—like polyalphamethylstyrene—undergo specific chain
scission with breakage occurring only at the ends. They literally unzip or depolymerize to become the
constituent monomer.

However, the degradation process can be useful from the viewpoints of understanding the structure of a
polymer or recycling/reusing the polymer waste to prevent or reduce environmentalpollution. Polylactic
acid and polyglycolic acid, for example, are two polymers that are useful for their ability to degrade under
aqueous conditions. A copolymer of these polymers is used for biomedical applications, such as
hydrolysable stitches that degrade over time after they are applied to a wound. These materials can also
be used for plastics that will degrade over time after they are used and will therefore not remain as litter.

The sorting of polymer waste for recycling purposes may be facilitated by the use of the Resin
identification codes developed by the Society of the Plastics Industry to identify the type of plastic.