國立清華大學材料科學工程學系

111 下學期課程

Materials Science and Engineering

II

Polymeric Materials PART I:

Basics/Polymerization/Structures

An-Chou Yeh/Andrew
葉安洲

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Basics:
 There are two types of polymers: plastics/elastomers (rubbers)
 Plastics are synthetic materials: thermoplastics & thermosets.
 They are generally lightweight, which reflects their composition: they are
organic materials, consisting mostly of carbon and hydrogen atoms.
 Polymers are usually transparent or translucid (or they have strong colors
because dyes have been incorporated in them) and excellent electric insulators.
Because their valence electrons reside in filled bands.
 Mechanically, polymers are much softer, weaker and less rigid than either metals
or ceramics. Clearly, a much weaker chemical bond is involved.

Polymerization:
The simplest polymer is polyethylene, the name: poly-ethylene means that its
structural unit is composed of many ethylene molecules (C2H4). Polyethylene is
synthesized by a chemical reaction involving a catalyst, which is a peroxide radical,
and ethylene gas. The peroxide attacks the double bond of ethylene and transforms the
latter into a radical (a molecule with an unsatisfied, chemically active, bond). Firstly,
lets get familiar with the notation of the bonding in the molecule.

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(a) (b)
Fig Covalent bonding in (a) ethylene molecule (b) activated ethylene molecule

The peroxide (H2O2) attacks the double bond of ethylene and transforms the latter
ethylene into a radical

The new ethylene molecule attacks other ethylene molecules in a similar way.

In general, there are 3 steps:

(1) Initiation: One of free radicals reacts with ethylene molecule to form new longer
chain free radical.

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(2) Propagation:

(3) Termination:

The process continues until a long molecule is formed, consisting of many thousands
of molecules; e.g. polyethylene which can be written as below, and the repeating unit
is called a “mer”.

The molecular weight of the polymer is the sum of all atomic weights, it is N times
the molecular weight of the mer. The molecular weight of ethylene is M = 2x12 + 4x1
= 28. With N = 10,000, the molecular weight of the polyethylene chain is 280,000. In
the processing of polymers, it is not possible to obtain all chains of the same length.
Thus, in practice, the molecular weight given for a polymer is an average value.

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Methods of Polymerizations:
1. Chain Polymerization (described above)
2. Stepwise Polymerization
Monomers chemically react with each other to produce linear polymers and a small
molecule of byproduct (condensation polymerization reactions).

3. Network polymerization
Chemical reaction takes place in more than two reaction sites (3D network).

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Structures:
Thermoplastics
Now let us look at the bonding of polyethylene. The bonds between the carbon atoms
in the chain and between the carbon and hydrogen are covalent and based on the sp3
hybrid valence electrons of carbon. This results in the shape of the molecule shown in
figure below. Zig-Zag configuration in ethylene is due to angle between carbon
covalent bonds (can be observed by AFM). These valence electrons completely fill
the valence band; therefore polymers are insulators.

When two polyethylene molecules approach, there is no sharing of valence electrons

between them. The bonding between the chains is a weak van der Waals bond. (In the
van der Waals bond, the charges of the valence electrons in one of the molecules repel
the electrons of the other so that the valence orbitals are slightly deformed. Small
electric dipoles are induced in the two approaching molecules. These dipoles attract

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each other weakly). The weakness of the van der Waals bond is responsible for the
softness of polyethylene. Other polymers, such as polyvinyl chloride (PVC) is built on
the same principle but with different mers.

PE

PVC
The structure of PVC is similar to that of polyethylene, except that one of the four
hydrogen atoms is replaced by chlorine. Chlorine has a high electronegativity and
attracts electron charge. The result is the formation of a permanent electric dipole in
each mer. When two PVC molecules are in proximity, this forms a secondary bond by
permanent dipoles, which is about 5 times stronger than the Van der Waals, but still 10
times weaker than the primary bonds described for metals and ceramics. The strength
of the permanent dipole bond is responsible for the fact that PVC is much stronger
than polyethylene.

Cl

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For thermoplastics: when they are heated, their thermal energy overcomes the weak
bonds between chains; the material becomes progressively softer until it liquefies. The
term "thermoplastic" indicates that the materials can be deformed by heating. The real
shape of a polyethylene molecule is not a straight bar. While the sp3 hybrid rigidly
imposes the angle of 109.5o between bonds, there is no obstacle to rotation of a bond
around its axis as illustrated below. Consequently, the polymer chains have an
irregular shape.

In a solid polymer, the individual chains are intertwined (like a plate of spaghetti).
This intertwining of the molecules has a large influence on the mechanical properties
of polymers. In particular, some polymers can not form the structure of a crystal, they
are amorphous; some do partially crystallized. Consequently, they do not have a
precise melting point.

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Thermosets
In thermosets, primary bonds are formed between the molecules. These primary
bonds between chains are called crosslinks. Thermoset polymers are synthesized by
a chemical reaction between two different substances. Usually, one of the
substances consists of large hydrocarbon molecules and is called the resin. The
other substance binds the resin molecules chemically together and is called the
hardener. With primary (strong) bonds between the chains, thermosets are stronger
and stable to somewhat higher temperatures than the thermoplastics. They do not

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soften at high temperatures but loose their hydrogen and transform into char at high
temperature. As a consequence, thermosets are not recyclable. There is a push from
the government to replace thermosets with thermoplastics as much as possible in
order to permit recycling.

Thermosets are used in some applications where high-temperature stability is essential.

They are also used as matrix in fiber-reinforced composites (fiber-glass or graphite
fibers) because the fabrication of large objects, such as boats, car bodies or airplane
parts vastly benefits from the ability of a thermoset to solidify at room temperature.
Lets examine one such thermoset:

Epoxy glue: When the epoxy is mixed with ethylene diamine, the oxygen bond is
opened and the reaction binds two epoxy molecules by covalent bonds.

Elastomers/Rubbers
Rubber is a natural or synthetic polymer with a molecular structure that allows it to
stretch by large amounts (coiled polymer molecule that deforms in the same way as a
coil spring). Rubber is a thermoplastic polymer with secondary bonds between the
chains. Natural rubber is too soft for many applications.
Strengthening rubber by reacting it with sulfur; the process is called vulcanization of
rubber. Sulfur reacts with the double bond in the rubber and establishes primary bonds
between the chains, effectively transforming the rubber into a thermoset,
vulcanization can be performed to any desired degree, producing rubber that is hard
enough for automotive tires.

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Thermoplastic nature of rubber Thermosetting rubber by vulcanization

Crystallinity:
Have you ever left a plastic bucket or some other plastic object outside during the
winter, and found that it cracks or breaks more easily than it would in the summer
time? What you experienced was the phenomenon known as the glass transition. This
transition is something that only happens to polymers, and is one of the things that
make polymers unique. The glass transition is pretty much what it sounds like; the
molecules can’t bend or readily move into different places, so materials become brittle.
There is a certain temperature (different for each polymer) called the glass transition
temperature, or Tg for short. When the polymer is cooled below this temperature, it
becomes hard and brittle, like glass. Some polymers are used above their glass
transition temperatures, and some are used below. Hard plastics like polystyrene and
poly(methyl methacrylate), are used below their glass transition temperatures; that is
in their glassy state. Their Tg's are well above room temperature, both at around 100
degree C. Rubber elastomers are used above their Tg's, that is, in the rubbery state,
where they are soft and flexible.

We have to make something clear at this point. The glass transition is not the same
thing as melting. Melting is a transition which occurs in crystalline polymers. Melting
happens when the polymer chains fall out of their crystal structures, and become a
disordered liquid. The glass transition is a transition which happens to amorphous
polymers; that is, polymers whose chains are not arranged in ordered crystals.

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Crystalline polymers will have a some amorphous portions. Structure of Partly
Crystalline Thermoplastics: depending on the constituents within a mer, polymers can
have an amorphous or crystalline/semicrystalline (partially crystalline) structure.
Amorphous polymers (a) lack order and are arranged in a random manner, while
semicrystalline polymers (b) are partially organized in orderly crystalline structures.

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Stereoisomerism: Same chemical composition but different structural arrangements.
Atactic stereoisomer: e.g. Pendent methyl group of polypropylene is randomly
arranged on either side of main carbon chain.

Isotactic stereoisomer:e.g. The pendent methyl group is always on same side of the
carbon chain.

Syndiotactic stereoisomer:e.g. The pendant group regularly alternates from one side
of the chain to the other side.

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