POLYMER
Polymer, any of a class of natural or synthetic substances
composed of very large molecules, called
macromolecules, that are multiples of simpler chemical
units called monomers. Polymers make up many of the
materials in living organisms, including, for
example, proteins, cellulose, and nucleic acids.
Moreover, they constitute the basis of such minerals
as diamond, quartz, and feldspar and such man-made
materials as concrete, glass, paper, plastics, and rubbers.
The word polymer designates an unspecified number
of monomer units. When the number of monomers is
very large, the compound is sometimes called a high
polymer. Polymers are not restricted to monomers of the
same chemical composition or molecular weight and
structure. Some natural polymers are composed of one
kind of monomer. Most natural and synthetic polymers,
however, are made up of two or more different types of
monomers; such polymers are known as copolymers.
Natural polymers
Organic and inorganic
Organic polymers play a crucial role in living things,
providing basic structural materials and participating in
vital life processes. For example, the solid parts of
all plants are made up of polymers. These include
cellulose, lignin, and various resins. Cellulose is
a polysaccharide, a polymer that is composed of sugar
molecules. Lignin consists of a complicated three-
dimensional network of polymers. Wood resins are
polymers of a simple hydrocarbon, isoprene. Another
familiar isoprene polymer is rubber.
polynucleotide chain of deoxyribonucleic acid (DNA)
Portion of polynucleotide chain of deoxyribonucleic acid
(DNA). The inset shows the corresponding pentose sugar
and pyrimidine base in ribonucleic acid (RNA).(more)
Other important natural polymers include the proteins,
which are polymers of amino acids, and the nucleic acids,
which are polymers of nucleotides—complex molecules
composed of nitrogen-containing bases, sugars,
and phosphoric acid. The nucleic acids carry genetic
information in the cell. Starches, important sources of
food energy derived from plants, are natural polymers
composed of glucose.
Many inorganic polymers also are found in nature,
including diamond and graphite. Both are composed
of carbon. In diamond, carbon atoms are linked in a
three-dimensional network that gives the material its
hardness. In graphite, used as a lubricant and in pencil
“leads,” the carbon atoms link in planes that can slide
across one another.
Synthetic polymers
Synthetic polymers are produced in different types of
reactions. Many simple hydrocarbons, such
as ethylene and propylene, can be transformed into
polymers by adding one monomer after another to the
growing chain. Polyethylene, composed of repeating
ethylene monomers, is an addition polymer. It may have
as many as 10,000 monomers joined in long coiled
chains. Polyethylene is crystalline, translucent, and
thermoplastic—i.e., it softens when heated. It is used for
coatings, packaging, molded parts, and the manufacture
of bottles and containers. Polypropylene is also
crystalline and thermoplastic but is harder than
polyethylene. Its molecules may consist of from 50,000
to 200,000 monomers. This compound is used in
the textile industry and to make molded objects.
Other addition polymers include
polybutadiene, polyisoprene, and polychloroprene,
which are all important in the manufacture of synthetic
rubbers. Some polymers, such as polystyrene, are glassy
and transparent at room temperature, as well as being
thermoplastic. Polystyrene can be coloured any shade
and is used in the manufacture of toys and
other plastic objects.
If one hydrogen atom in ethylene is replaced by
a chlorine atom, vinyl chloride is produced. This
polymerizes to polyvinyl chloride (PVC), a colourless,
hard, tough, thermoplastic material that can be
manufactured in a number of forms, including foams,
films, and fibres. Vinyl acetate, produced by the reaction
of ethylene and acetic acid, polymerizes to amorphous,
soft resins used as coatings and adhesives. It
copolymerizes with vinyl chloride to produce a large
family of thermoplastic materials.
Many important polymers
have oxygen or nitrogen atoms, along with those
of carbon, in the backbone chain. Among such
macromolecular materials with oxygen atoms
are polyacetals. The simplest polyacetal
is polyformaldehyde. It has a high melting point and is
crystalline and resistant to abrasion and the action
of solvents. Acetal resins are more like metal than are
any other plastics and are used in the manufacture of
machine parts such as gears and bearings.
A linear polymer characterized by a repetition of ester
groups along the backbone chain is called a polyester.
Open-chain polyesters are colourless, crystalline,
thermoplastic materials. Those with high molecular
weights (10,000 to 15,000 molecules) are employed in
the manufacture of films, molded objects, and fibres
such as Dacron.
Polymer Synthesis
Polymers are a class of materials comprising small
repeating chemical units. The building block or the
repeating unit in the polymer is called a monomer.
Polymerization, or polymer synthesis, is a chemical
reaction in which monomers are joined together by
covalent bonding to form polymer structures. The length
of the polymer chain is characterized by the number of
repeating units in the chain, which is referred to as
degree of polymerization (DP). The molecular weight of
the polymer is the product of the molecular weight of the
repeating unit and the DP. The basic properties inherent
to polymers mainly depend on the molecular weight,
structure (linear or branched), and DP. Based on the
types of chemical reaction involved, polymerizations are
grouped into two types, known as condensation and
addition polymerization. In condensation or step-growth
polymerization, a condensation reaction takes place
between two different bi-functional or tri-functional
monomers to produce polymers, whereby small
molecules, often water, are eliminated from the reaction.
In addition polymerization, or chain-growth
polymerization, the growth of the polymer occurs by
adding monomers to active sites on the polymer chain
with regeneration of the active sites at the end of each
growth step. An initiator is required to produce the
initiator species with reactive centers. The reactive
center can be a free radical, cation, anion, or
organometallic complex.
The characteristics of polymers are highly dependent on
monomer types and the polymerization method used for
the synthesis. Living radical polymerization, also referred
to as controlled radical polymerization (CRP), enables
better control over the polymer molecular weight,
molecular weight distribution, functionality, and
composition. CRP can be utilized with a wide range of
vinyl monomers to build polymers with diverse
properties for different applications.
There are three fundamental CRP techniques:
• Atom transfer radical polymerization (ATRP)
• Reversible addition/fragmentation chain transfer
(RAFT) polymerization
• Nitroxide-mediated polymerization (NMP)
ATRP is well-suited for surface modification applications
which rely on tailored hydrophilicity, adhesive
properties, or nanoparticle functionalization. Polymers
derived from both RAFT and ATRP can be modified post-
polymerization and are used extensively in the
biomedical field for drug delivery and tissue engineering
applications. Block copolymers for biomedical
applications, are commonly developed from RAFT or
ATRP. Block copolymers, developed from NMP, are
essential for pigment dispersion, memory devices, and
composite manufacturing.
Polymer characterization
Polymer characterization is the analytical branch
of polymer science.
The discipline is concerned with the characterization of
polymeric materials on a variety of levels. The
characterization typically has as a goal to improve the
performance of the material. As such, many
characterization techniques should ideally be linked to
the desirable properties of the material such as strength,
impermeability, thermal stability, and optical properties.
Characterization techniques are typically used to
determine molecular mass, molecular structure,
morphology , thermal properties, and mechanical
properties.
Molecular mass
The molecular mass of a polymer differs from typical
molecules, in that polymerization reactions produce a
distribution of molecular weights and shapes. The
distribution of molecular masses can be summarized by
the number average molecular weight, weight average
molecular weight, and polydispersity. Some of the most
common methods for determining these parameters
are colligative property measurements, static light
scattering techniques, viscometry, and size exclusion
chromatography.
Gel permeation chromatography, a type of size exclusion
chromatography, is an especially useful technique used
to directly determine the molecular weight distribution
parameters based on the polymer's hydrodynamic
volume. Gel permeation chromatography is often used in
combination with multi-angle light
scattering (MALS), Low-angle laser light
scattering (LALLS) and/or viscometry for an absolute
determination (i.e., independent of the chromatographic
separation details) of the molecular weight distribution
as well as the branching ratio and degree of long chain
branching of a polymer, provided a suitable solvent can
be found.
Molar mass determination of copolymers is a much more
complicated procedure. The complications arise from the
effect of solvent on the homopolymers and how this can
affect the copolymer morphology. Analysis of
copolymers typically requires multiple characterization
methods. For instance, copolymers with short chain
branching such as linear low-density polyethylene (a
copolymer of ethylene and a higher alkene such as
hexene or octene) require the use of Analytical
Temperature Rising Elution Fractionation (ATREF)
techniques. These techniques can reveal how the short
chain branches are distributed over the various
molecular weights. A more efficient analysis of
copolymer molecular mass and composition is possible
using GPC combined with a triple-detection system
comprising multi-angle light scattering, UV absorption
and differential refractometry, if the copolymer is
composed of two base polymers that provide different
responses to UV and/or refractive index.
Molecular structure
Many of the analytical techniques used to determine the
molecular structure of unknown organic compounds are
also used in polymer characterization. Spectroscopic
techniques such as ultraviolet-visible
spectroscopy, infrared spectroscopy, Raman
spectroscopy, nuclear magnetic resonance
spectroscopy, electron spin resonance spectroscopy, X-
ray diffraction, and mass spectrometry are used to
identify common functional groups.
Morphology
Polymer morphology is a microscale property that is
largely dictated by the amorphous or crystalline portions
of the polymer chains and their influence on each other.
Microscopy techniques are especially useful in
determining these microscale properties, as the domains
created by the polymer morphology are large enough to
be viewed using modern microscopy instruments. Some
of the most common microscopy techniques used are X-
ray diffraction, Transmission Electron
Microscopy, Scanning Transmission Electron
Microscopy, Scanning Electron Microscopy, and Atomic
Force Microscopy.
Polymer morphology on a mesoscale (nanometers to
micrometers) is particularly important for the mechanical
properties of many materials. Transmission Electron
Microscopy in combination with staining techniques, but
also Scanning Electron Microscopy, Scanning probe
microscopy are important tools to optimize the
morphology of materials like polybutadiene-
polystyrene polymers and many polymer blends.
X-ray diffraction is generally not as powerful for this class
of materials as they are either amorphous or poorly
crystallized. The Small-angle scattering like Small-angle X-
ray scattering (SAXS) can be used to measure the long
periods of semicrystalline polymers.
Thermal properties
A true workhorse for polymer characterization is thermal
analysis, particularly Differential scanning calorimetry.
Changes in the compositional and structural parameters
of the material usually affect its melting transitions or
glass transitions and these in turn can be linked to many
performance parameters. For semicrystalline polymers it
is an important method to measure
crystallinity. Thermogravimetric analysis can also give an
indication of polymer thermal stability and the effects of
additives such as flame retardants. Other thermal
analysis techniques are typically combinations of the
basic techniques and include differential thermal
analysis, thermomechanical analysis, dynamic
mechanical thermal analysis, and dielectric thermal
analysis.
Dynamic mechanical spectroscopy and dielectric
spectroscopy are essentially extensions of thermal
analysis that can reveal more subtle transitions with
temperature as they affect the complex modulus or the
dielectric function of the material.
Mechanical properties
The characterization of mechanical properties in
polymers typically refers to a measure of the strength,
elasticity, viscoelasticity, and anisotropy of a polymeric
material. The mechanical properties of a polymer are
strongly dependent upon the Van der Waals interactions
of the polymer chains, and the ability of the chains to
elongate and align in the direction of the applied force.
Other phenomena, such as the propensity of polymers to
form crazes can impact the mechanical properties.
Typically, polymeric materials are characterized as
elastomers, plastics, or rigid polymers depending on their
mechanical properties.
The tensile strength, yield strength, and Young's
modulus are measures of strength and elasticity, and are
of particular interest for describing the stress-strain
properties of polymeric materials. These properties can
be measured through tensile
testing. For crystalline or semicrystalline polymers,
anisotropy plays a large role in the mechanical properties
of the polymer. The crystallinity of the polymer can be
measured through differential scanning calorimetry. For
amorphous and semicrystalline polymers, as stress is
applied, the polymer chains are able to disentangle and
align. If the stress is applied in the direction of chain
alignment, the polymer chains will exhibit a higher yield
stress and strength, as the covalent bonds connecting
the backbone of the polymer absorb the stress. However,
if the stress is applied normal to the direction of chain
alignment, the Van der Waals interactions between
chains will primarily be responsible for the mechanical
properties and thus, the yield stress will decrease. This
would be observable in a stress strain graph found
through tensile testing. Sample preparation, including
chain orientation within the sample, for tensile tests
therefore can play a large role in the observed
mechanical properties.
The fracture properties of crystalline and semicrystalline
polymers can be evaluated with Charpy impact testing.
Charpy tests, which can also be used with alloy systems,
are performed by creating a notch in the sample, and
then using a pendulum to fracture the sample at the
notch. The pendulum’s motion can be used to
extrapolate the energy absorbed by the sample to
fracture it. Charpy tests can also be used to evaluate the
strain rate on the fracture, as measured with changes in
the pendulum mass. Typically, only brittle and somewhat
ductile polymers are evaluated with Charpy tests. In
addition to the fracture energy, the type of break can be
visually evaluated, as in whether the break was a total
fracture of the sample or whether the sample
experienced fracture in only part of the sample, and
severely deformed section are still connected.
Elastomers are typically not evaluated with Charpy tests
due to their high yield strain inhibiting the Charpy test
results.
There are many properties of polymeric materials that
influence their mechanical properties. As the degree of
polymerization goes up, so does the polymer’s strength,
as a longer chains have high Van der Waals interactions
and chain entanglement. Long polymers can entangle,
which leads to a subsequent increase in bulk
modulus. Crazes are small cracks that form in a polymer
matrix, but which are stopped by small defects in the
polymer matrix. These defects are typically made up of a
second, low modulus polymer that is dispersed
throughout the primary phase. The crazes can increase
the strength and decrease the brittleness of a polymer by
allowing the small cracks to absorb higher stress and
strain without leading to fracture. If crazes are allowed to
propagate or coalesce, they can lead to cavitation and
fracture in the sample. Crazes can be seen with
transmission electron microscopy and scanning electron
microscopy, and are typically engineered into a
polymeric material during synthesis. Crosslinking,
typically seen in thermoset polymers, can also increase
the modulus, yield stress, and yield strength of a
polymer.
Dynamic mechanical analysis is the most common
technique used to characterize viscoelastic behavior
common in many polymeric systems. DMA is also
another important tool to understand the temperature
dependence of polymers’ mechanical behavior. Dynamic
mechanical analysis is a characterization technique used
to measure storage modulus and glass transition
temperature, confirm crosslinking, determine switching
temperatures in shape-memory polymers, monitor cures
in thermosets, and determine molecular weight. An
oscillating force is applied to a polymer sample and the
sample’s response is recorded. DMA documents the lag
between force applied and deformation recovery in the
sample. Viscoelastic samples exhibit a sinusoidal modulus
called the dynamic modulus. Both energy recovered and
lost are considered during each deformation and
described quantitatively by the elastic modulus (E’) and
the loss modulus (E’’) respectively. The applied stress and
the strain on the sample exhibit a phase difference, ẟ,
which is measured over time. A new modulus is
calculated each time stress is applied to the material, so
DMA is used to study changes in modulus at various
temperatures or stress frequencies.
Other techniques include viscometry, rheometry, and
pendulum hardness.
