Polymers

BS Civil Engineering
Properties and Characterization of
Polymers
• A polymer is a molecular compound that can be distinguished
by a high molar mass, ranging into thousands and even millions
of mass and they are made up of many repeating units.
Properties and Characterization of
Polymers
• Synthetic (man-made) polymers were first developed in the
early 20th century, and these polymers remarkably transformed
our world as different materials can be created with properties
that are ideal for different applications.
• Natural polymers have been around since life itself began.
Cellulose, starch, and other complex carbohydrates are
examples of natural polymers. Natural rubber is a polymer
obtained from rubber trees and even the code for life itself,
DNA, is a natural polymer.
Properties and Characterization of
Polymers
• Monomers (mono meaning “one”;
meros meaning “unit”) are the small
molecules that are used for
synthesizing polymers and each
monomer is analogous to a link in a
chain. Monomers, simple repeating
units, and this type of composition
markedly restrict the number of
possible isomers.
• Polymers (poly means “many”) can be
created from one monomer, or from a
combination of two or more different
monomers.
Properties and Characterization of
Polymers
• If a polymer is made up of only one
type of monomer (e.g.
polyethylene), then it is known as a
homopolymer.
• Other homopolymers that are
synthesized by the radical
mechanism are TeflonTM,
polytetrafluoroethylene, and
poly(vinyl chloride) (PVC).
Properties and Characterization of
Polymers
• Synthetic polymers can be made from many different starting
materials which usually come from crude oil (raw material).
Presently, crude oil is the starting material for many plastics,
pharmaceuticals, fabrics, and other carbon-based products.
Polymer Molecule
• The molecules in polymers are gigantic and because of their
size, they are often referred to as macromolecules.
• The backbone of each carbon-chain polymer is a string of carbon
atoms and within each molecule, the atoms are bound together
by covalent interatomic bonds.
Polymer Molecule
• Many times, each carbon atom singly bonds to two adjacent
carbon atoms on either side which is represented as follows:

• Each of the two remaining valence electrons for every carbon

atom may be involved inside bonding with atoms or radicals
that are positioned adjacent to the chain. Of course, both chain
and side double bonds are also possible.
The Chemistry of Polymer Molecule
• The hydrocarbon ethylene (C2H4) is a gas at ambient
temperature and pressure which has the following molecular
structure:
The Chemistry of Polymer Molecule
• Under appropriate conditions, ethylene gas reacted, and it will
transform to polyethylene (PE) which is a solid polymeric
material. This process begins when an active center is formed
by the reaction between an initiator or catalyst species (R·) and
the ethylene monomer, as follows:
The Chemistry of Polymer Molecule
• Next, the polymer chain forms by the sequential addition of
monomer units to this actively growing chain molecule which is
represented schematically as follows:
The Chemistry of Polymer Molecule
• After the addition of many • or alternatively as:
ethylene monomer units, the
result is the polyethylene
molecule. Representation of
polyethylene chain structure
is shown below: • Here, the repeat units are
enclosed in parentheses, and
the subscript n indicates the
number of times it repeats.
The Chemistry of Polymer Molecule

• For polyethylene, (a) a schematic representation of repeat unit

and chain structures, and (b) a perspective of the molecule,
indicating the zigzag backbone structure (Callister & Rethwisch,
2014).
The Chemistry of Polymer Molecule
• Other chemistry of polymer structures such as
tetrafluoroethylene monomer to form polytetrafluoroethylene
(PTFE) is shown below:

• Polytetrafluoroethylene (having the trade name Teflon) belongs

to a family of polymers called fluorocarbons.
The Chemistry of Polymer Molecule
• The vinyl chloride monomer (CH2=CHCl) is a slight variant of
that for ethylene, in which one of the four H atoms is replaced
with a Cl atom. Its polymerization is represented as:

• and leads to poly(vinyl chloride) (PVC), another common

polymer.
The Chemistry of Polymer Molecule
• Some polymers may be represented using the following
generalized form:

• where the R represents either an atom [i.e., H or Cl, for

polyethylene or poly(vinyl chloride), respectively] or an organic
group such as CH3, C2H5, and C6H5 (methyl, ethyl, and phenyl).
The Chemistry of Polymer Molecule
• Repeat unit and chain
structures for
a. Polytetrafluoroethylene,
b. Poly(vinyl chloride), and
c. Polypropylene

(Callister & Rethwisch, 2014).

Molecular Structures of Polymers
• Molecular weight and shape of a polymer is not the only basis
of its physical characteristics, the difference in the structure of
the molecular chains must also be considered.
• Table 1. Description and schematic representations of linear,
branched, crosslinked, and network (three-dimensional)
molecular structures. Circles designate individual repeat units.
Molecular Structures of Polymers
Molecular Structures of Polymers
Molecular Structures of Polymers

• Note that polymers may have more than one distinctive

structural type, for example, a linear polymer may have limited
branching and crosslinking.
Common Polymeric Materials
• Presently, there are more than 60,000 synthetic polymers
known, with this, six types of polymers (Table 2) account for
roughly 75% of those used in both Europe and the United
States.
• Table 2. Six Common Polymers (Symbols retrieved from:
https://www.acmeplastics.com/content/your-guide-to-plastic-
recycling-symbols/)
Common Polymeric Materials
Common Polymeric Materials
Common Polymeric Materials
Common Polymeric Materials
Common Polymeric Materials
Molecular Weight and Degree of
Polymerization
• Polymers with very long chains have extremely large molecular
weights but during the polymerization process, not all polymer
chains will grow to the same length, and this results in a
distribution of chain lengths or molecular weights.
• Usually, an average molecular weight is specified, which can be
determined by the measurement of various physical properties
such as viscosity and osmotic pressure.
Molecular Weight and Degree of
Polymerization
• There are several ways of defining average molecular weight.
The number-average molecular weight Mn is obtained by
dividing the chains into a series of size ranges and then
determining the number fraction of chains within each size
range.
Molecular Weight and Degree of
Polymerization
• The number- average molecular weight is expressed as:

• where Mi represents the mean (middle) molecular weight of

size range i, and Xi is the fraction of the total number of chains
within the corresponding size range.
Molecular Weight and Degree of
Polymerization
• A weight-average molecular weight Mw is based on the weight
fraction of molecules within the various size ranges. It is
calculated according to:

• where, again, Mi is the mean molecular weight within a size

range, whereas Wi denotes the weight fraction of molecules
within the same size interval.
Degree of Polymerization
• Degree of Polymerization (DP) is an alternative way of
expressing the average chain size of a polymer. DP represents
the average number of repeat units in a chain, and it is related
to the number-average molecular weight Mn by the equation:

• where m is the repeat unit molecular weight.

Degree of Polymerization

• Hypothetical polymer molecule size distributions on the basis

of (a) number and (b) weight fractions of molecules
Degree of Polymerization
• The length of polymer chains has affected many polymer
properties. For example, as the molecular weight (about 100,000
g/mol) of a polymer increases, its melting or softening
temperature also increases.
• But for polymers with very short chains or having molecular
weights on the order of 100 g/mol, will usually exist as liquids
at room temperature.
Degree of Polymerization
• Those with molecular weights of approximately 1000 g/mol
exist as waxy solids (e.g., paraffin wax) and soft resins.
• For polymers with molecular weights ranging between 10,000
and several million g/mol that exist as solids, are sometimes
termed high polymers.
• Therefore, the same polymer material can acquire various
properties if it is produced with different molecular weights.
Degree of Polymerization
• Example: Assume that the molecular weight distributions shown
in Figure 3 are for poly(vinyl chloride). For this material,
compute (a) the number-average molecular weight, (b) the
degree of polymerization, and (c) the weight-average molecular
weight.
• Data to be used for Number/Weight-Average Molecular Weight
Computations in Example 1.
Degree of Polymerization
Thermoplastic and Thermosetting
Polymers
• Molecular structure has a great effect on how polymers react to
mechanical forces at elevated temperatures. Indeed, one
classification for these materials is according to behavior with rising
temperature.
• Thermoplastics (or thermoplastic polymers) and thermosets
(or thermosetting polymers) are the two subdivisions.
Thermoplastic Polymers
• Thermoplastics soften upon heating and later liquefy, then it
hardens when cooled.
• This process is reversible and can be repeated.
• Exposure of a molten thermoplastic polymer to very high-
temperature results in irreversible degradation. Examples of
common thermoplastic polymers are polyethylene, polystyrene,
poly(ethylene terephthalate), and poly(vinyl chloride).
Thermosetting Polymers
• Thermosetting polymers are network polymers, they do not
soften upon heating, and they become permanently hard during
their formation.
• Network polymers have covalent crosslinks between adjacent
molecular chains.
• During heat treatment, the bonds fasten the chains together to
resist the vibrational and rotational chain motions at high
temperatures. Therefore, the materials do not soften when
heated.
Thermosetting Polymers
• Excessive heating temperatures will cause severance of these crosslink
bonds and polymer degradation. As compared to thermoplastics,
these thermoset polymers are generally harder and stronger and have
better dimensional stability. Examples of these thermosets
(crosslinked and network polymers) are vulcanized rubbers,
epoxies, phenolics, and some polyester resins.
Copolymers
• A copolymer is composed of two repeat units as represented in
Table 3. It is possible that there are different sequencing
arrangements along the polymer chains which depends on the
polymerization process and the relative fractions of these repeat
unit types. Synthetic rubbers are usually copolymers.
• Table 3. Schematic representations of random, alternating,
block, and graft copolymers. The two different repeat unit types
are designated by blue and red circles
Copolymers
Polymer Crystallinity
• In crystalline state, the atomic arrangement in polymer
materials are more complex as compared to metals and
ceramics because in polymers it involves molecules instead of
just atoms or ions.
• Polymer crystallinity is the packing of molecular chains to
produce an ordered atomic array. Crystal structures may be
specified in terms of unit cells, which are often quite complex.
• Figure 4 shows the example of a unit cell for polyethylene and
its relationship to the molecular chain structure (the unit has
orthorhombic geometry).
Polymer Crystallinity
• Unit cell for polyethylene and
its relationship to the
molecular chain structure (the
unit has orthorhombic
geometry).
Polymer Crystallinity
• Polymer molecules are often partially crystalline (or
semicrystalline), having crystalline regions dispersed within the
remaining amorphous material.
• An amorphous region is the result of any chain disorder or
misalignment, a case that is quite common because twisting,
kinking, and coiling of the chains hinder the strict ordering of
every segment of every chain.
• The extent of crystallinity may range from completely
amorphous to almost entirely (up to about 95%) crystalline. If
compared to metal specimens (almost always entirely
crystalline) and many ceramics (either totally crystalline or
totally non-crystalline) polymeric materials behave differently.