Engineering Materials

Ch.E 311
Lecture 10
Polymeric and Composite Materials
Polymers
• Polymers – materials consisting of polymer molecules that consist of
repeated chemical units (`mers') joined together, like beads on a string.
Some polymer molecules contain hundreds or thousands of monomers
and are often called macromolecules.
• Polymers may be natural , such as leather, rubber, cellulose or DNA, or
synthetic , such as nylon or polyethylene.
• 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• In some applications metal and wood parts have been replaced by plastics,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.
 Hydrocarbon molecules (I)
• Most polymers are organic in their origin and are formed from
hydrocarbon molecules
• Each C atom has four electrons that participate in bonds, each H atom
has one bonding electron
• Examples of saturated (all bonds are single ones) hydrocarbon
molecules:
Hydrocarbon molecules (II)
• Double and triple bonds can exist between C
atoms (sharing of two or three electron
pairs). Molecules with double and triple
bonds are called unsaturated.
• Isomers are molecules that have the same
composition (contain the same atoms) but
have different atomic arrangement. An
example is butane and isobutene.
• Physical properties (e.g. boiling temperature) depend on the isomeric
state. for example, the boiling temperatures for normal butane and
isobutane are 0.5 and 12.3oC respectively.
• Boiling temperatures rise with increasing molecular weight as shown
in Table.
Hydrocarbon molecules (III)
• Many other organic groups
can be involved in in polymer
structures.
• In table below R and R’
represent organic groups
such as CH3, C2H5, and C6H5
(methyl, ethyl, and phenyl).
Polymer Molecules
• Polymer molecules can be very large (macromolecules)
• Most polymers consist of long and flexible chains with a string of C
atoms as a backbone.
• Side-bonding of C atoms to H atoms or radicals
• Double bonds are possible in both chain and side bonds
• Repeat unit in a polymer chain (“unit cell”) is a mer.
• Small molecules from which polymer is synthesized is monomer. A
single mer is sometimes also called a monomer.
Chemistry of polymer molecules
• Consider again the hydrocarbon ethylene (C2H4), which is a gas at
ambient temperature and pressure and has the following molecular
structure:

• If the ethylene gas is reacted under appropriate conditions, it will

transform to polyethylene (PE), which is a solid polymeric material.
• Ethylene transform to polyethylene (solid) by forming active mer
through reaction with initiator or catalytic radical (R.).
• (.) denotes unpaired electron (active site)
This polyethylene chain structure can also be represented as:
n indicates the number of repeating units
Chemistry of polymer molecules (II)
• When all mers are the same, the molecule is
called a homopolymer
• When there is more than one type of mer
present, the molecule is a copolymer.
• Mer units that have 2 active bonds sites to
connect with other mers are called
bifunctional
• Mer units that have 3 active bonds sites to
connect with other mers are called
trifunctional. They form three-dimensional
molecular network structures
Chemistry of polymer molecules II
Molecular Weight
• Many polymer properties are affected by the length of the polymer chains.
• For example, the melting or softening temperature increases with increasing molecular
weight (for up to about 100,000 g/mol).
• At room temperature, polymers with very short chains (having molecular weights on the
order of 100 g/mol) will generally exist as liquids.
• Those with molecular weights of approximately 1000 g/mol are waxy solids (such as
paraffin wax) and soft resins.
• Solid polymers (termed as high polymers) have molecular weights ranging between
10,000 and several million g/mol.
• Thus, the same polymer material can have quite different properties if it is produced
with a different molecular weight.
• Other properties that depend on molecular weight include elastic modulus and strength.
Determination of Molecular Weight
• The molecular weight (chain length) is controlled by the synthesis
process:
• Relative rates of initiation
• Propagation
• Termination
• During the polymerization process, not all polymer chains will grow to
the same length; this results in a distribution of chain lengths.
• There are several ways of defining average molecular weight.
Number Average Molecular Weight
• The number average molecular weight is obtained by dividing the
chains into a series of size ranges and then determining the number
fraction of chains within each size range.
• 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.
Weight Average Molecular Weight
• A weight-average molecular weight is based on the
weight fraction of molecules within the various size
ranges.

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
• An alternate way of expressing average chain size of a polymer is as
the degree of Polymerization, DP, which represents the average
number of repeat units in a chain.

where m is the repeat unit molecular weight.

Molecular Shape
• Polymer molecules not only show linear chains but also exhibit zigzag arrangement of the
backbone atoms. Single chain bonds are capable of rotating and bending in three dimensions.
• Consider the chain atoms in the figure. The angle between the singly bonded carbon atoms is
~109o – carbon atoms form a zigzag pattern in a polymer molecule.
• Moreover, while maintaining the 109o angle between bonds polymer chains can rotate around
single C-C bonds.
• Random kinks and coils lead to entanglement in the molecular chains like a spaghetti
structure.
• Neighboring chains may intertwine and entangle. Large elastic extensions of rubbers
correspond to unraveling of these coiled chains.
• Mechanical / thermal characteristics depend on the ability of chain segments rotation.
• For example, the region of a chain segment that has a double bond is rotationally rigid.
• Also, introduction of a bulky or large side group of atoms restricts rotational movement. For
example, polystyrene molecules, which have a phenyl side group are more resistant to
rotational motion than are polyethylene chains.
Molecular Structure
The physical characteristics of polymer material depend not only on
molecular weight and shape, but also on molecular structure:

Types of
Polymers

Linear Branched Crosslinked Network

Polymers Polymers Polymers Polymers
Linear Polymers
• LP are those in which the repeat units are joined together end to end
in single chains. These long chains are flexible and Van der Waals and
hydrogen bonding between the chains.
• Examples polyethylene, poly(vinyl chloride), polystyrene, nylon.
 Branched Polymers
• Polymers may be synthesized in which side-branch chains are
connected to the main ones.
• The branches, considered to be part of the main- chain
molecule, which may result from side reactions that occur
during the synthesis of the polymer.
• The chain packing efficiency is reduced with the formation of
side branches, which results in a lowering of the polymer
density.
• Example: High-density polyethylene (HDPE) is Primarily a
linear polymer, whereas low-density polyethylene (LDPE)
contains short chain branches.
• LDPE : soft and pliable – (common example is plastic bags)
• HDPE: Rigid than LDPE – (common example is bottles, and bottle caps)
Crosslinked Polymers
• In CP, adjacent linear chains are joined one to another at various
positions by covalent bonds.
• Often, this crosslinking is accomplished by additive atoms or
molecules that are covalently bonded to the chains.
• Many of the rubber elastic materials are crosslinked; in rubbers, this is
called vulcanization.
Network Polymers
• Actually, a polymer that is highly crosslinked may also be classified as a
network polymer.
• Multifunctional monomers forming three or more active covalent bonds
make three-dimensional networks and are termed network polymers.
• These materials have distinctive mechanical and thermal properties;
Examples include epoxies, polyurethanes, and phenol-formaldehyde (PF ).
• The properties of network polymers depend on the density of the
network. Polymers having a dense network, such as PF resin, are very
rigid—even brittle—whereas network polymers containing long, flexible
branches connected at only a few sites along the chains exhibit elastic
properties.
Classification Scheme for the
Characteristics of Polymer Molecules
 Classification in response to rising
Temperature
• The response of a polymer to mechanical
forces at elevated temperatures is related Behavior to
to its dominant molecular structure. Temperature
rise

Thermoplastic Thermosetting
Thermoplastics
• Thermoplastics soften when heated (and eventually liquefy) and harden when
cooled—processes 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.
• 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.
• Examples of common thermoplastic polymers include polyethylene, polystyrene,
poly(ethylene terephthalate), and poly(vinyl chloride).
Thermosets
• 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.
Copolymers
 Polymer Crystallinity
• 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.
• For example, Figure 14.10 shows the unit cell for
polyethylene and its relationship to the molecular
chain structure; this unit cell has orthorhombic
geometry.
• Of course, the chain molecules also extend beyond the
unit cell shown in the figure.
• Molecular substances having small molecules (e.g., water and
methane) are normally either totally crystalline (as solids) or totally
amorphous (as liquids).
• The degree of crystallinity may range from completely amorphous to
almost entirely (up to about 95%) crystalline.
• Metal specimens are almost always entirely crystalline, whereas
many ceramics are either totally crystalline or totally noncrystalline.
• Semicrystalline polymers are, in a sense, analogous to two-phase
• metal alloys.
• The density of a crystalline polymer will be greater than an
amorphous one of the same material and molecular weight, since the
chains are more closely packed together for the crystalline structure.
Degree of crystallinity
• The degree of crystallinity by weight may be determined from accurate
density measurements, according to:

• where ρs is the density of a specimen for which the percent crystallinity

is to be determined, ρa is the density of the totally amorphous polymer,
and ρc is the density of the perfectly crystalline polymer.
• The values of ρa and ρc must be measured by other experimental means.
Given, L=0.741nm, W= 0.494nm, H=0.255nm
Stress Strain behavior of Polymers
• Three typically different types of stress–strain behavior are found for
polymeric Materials:
• Curve A illustrates the stress–strain character for a brittle polymer, in
as much as it fractures while deforming elastically.
• The behavior for a plastic material, curve B, is similar to that for many
metallic materials; the initial deformation is elastic, which is followed
by yielding and a region of plastic deformation.
• Finally, the deformation displayed by curve C is totally elastic; this
rubber-like elasticity (large recoverable strains produced at low stress
levels) is displayed by a class of polymers termed the elastomers.
Reference
• Chapter 14 Polymer Structures
• Chapter 15 Characteristics, Applications, and Processing of Polymers
• Material Science And Engineering - An Introduction By William D.
Callister.