Conducting polymers information sheet

Most textbooks indicate that one of the most important properties of polymers is that
they are electrical insulators – they are used for covering electrical cables, the bodies
of electrical plugs and sockets, and so on. This is no longer completely true. Over the
past few years several polymeric materials have been produced that conduct
electricity and a range of applications is being developed. These conducting
polymers are of two basic types:

▼ intrinsically conducting polymers where the polymeric material itself

conducts; and
▼ extrinsically conducting polymers which are composites where a conductive
material such as carbon black is embedded in a non-conducting polymer such
as poly(ethene).

Intrinsically conducting polymers

The simplest intrinsically conducting polymer is poly(ethyne), sometimes called
poly(acetylene), (see below) which, despite its name, is an alkene not an alkyne. It
consists of a hydrocarbon chain with alternating single and double bonds; called a
conjugated system. The p-orbitals which form the double bonds can overlap to form
a delocalised π−system (similar to the one in benzene). Electrons flow through the
delocalised system and so the polymer can conduct. In fact, additives such as iodine
have to be incorporated to maximise the conductivity by ensuring that the polymer
does exist in the delocalised form rather than as localised single and double bonds.
Suitably doped poly(ethyne) can have a conductivity comparable with that of copper
provided the material has been stretched to align the chains so that they all run in the
same direction. Poly(ethyne) has problems for everyday applications as it is attacked
by oxygen from the air but other more stable polymers with conjugated systems also
have conducting properties. There are some examples on the next page.

H C C H H C C H H C C H ethyne

H H H H H H

C C C C C C poly(ethyne)

H H H
Delocalised π-system

C C C C C C

H H H

Poly(ethyne)

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 (CH2) –R
n

NH

n
S
n n
Poly(ethyne) Poly(alkylthiophene) Poly(aniline)

S N O
n n n
Poly(thiophene) H Poly(furan)

Poly(pyrrole)

Examples of intrinsically conducting polymers

The well-known conductivity of graphite (see below) can be explained in the

same way. Here there is a two-dimensional delocalised system covering a layer of
carbon atoms so that graphite conducts well along the planes of carbon atoms but
poorly at right angles to them.

Delocalised π-system
C C C
C C
C C C
C C

Graphite

Extrinsically conducting polymers

One type of extrinsically conducting polymer consists of a matrix of poly(ethene)
with a percentage of conducting carbon black (a form of powdered graphite)
incorporated in it. If the carbon black particles are close enough to be in contact with
one another, the material conducts. If the particles are not in contact, it is an
insulator. This means that the degree of electrical conduction depends on
temperature. At high temperature, the poly(ethene) matrix expands and pulls the
particles of carbon black away from each other, decreasing the conductivity. At
lower temperatures the poly(ethene) contracts, the carbon black particles are closer
and the material conducts well. This temperature dependence of conductivity leads
to the use of this material in self-regulating heater cable and PolySwitch* re-settable
circuit protection devices.

* PolySwitch is a registered trademark of Raychem Corporation.

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 ‡
Beat the freeze – the IceStop system
Ice can cause a lot of damage – burst pipes, slippery walkways, collapsing roofs - all
of which can be prevented by low level heating. Conventional heating circuits have
some disadvantages here as they have a constant current which can result in ‘hot
spots’ and energy wastage. The IceStop system consists of parallel copper wires
embedded in a conducting polymer. Carbon granules form conducting pathways
between the wires resulting in a large number of miniature parallel circuits. The
polymer conducts electricity well and thus acts as a heater, only when it is cold. As
the material warms up the poly(ethene) expands, interrupting some of the conducting
pathways and switching off the miniature circuits (see below).

+ –
Power supply

Polymer holds the

carbon black particles
in place

Carbon black particles

Current-carrying
electrodes

Conducting pathway
of carbon black
particles

Heat is generated only where electric current flows

through the carbon black pathways

‡
IceStop is a registered trademark of Raychem Corporation.

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 COLD

Heat generated by flowing current

Electrically
insulating layers

Conducting pathway
of carbon black particles
Current carrying
electrode
+ —
Cold polymer

HOT

When heated the polymer expands.

This separates the carbon black
particles, breaking the conducting pathway

Carbon black
particles
separated by
expansion + —
Expanded hot
polymer

Heater cable

IceStop cable can be laid along water pipes, under pathways and along guttering
to provide low-level, self-regulating heating which keeps the environment frost-free.
It is flexible and easy to install, can be cut to any length required and can be
overlapped or wound round a pipe.

Protecting batteries – the PolySwitch device

Lithium batteries are used in many small hand-held electrical appliances such as
cameras but a current overload can lead to overheating resulting in, at best, damage
to the appliance, and, at worst, the battery exploding. Lithium batteries are also used
in telecom systems, audio speakers, fire and burglar alarms and personal computers.
A conventional fuse could provide the required protection but needs to be replaced if
it blows. A PolySwitch device does the same job but can be reset, rather than having
to be replaced, once the fault has been rectified. As in IceStop cable, carbon granules
form conducting pathways through the polymer and these pathways are broken if the
material becomes too warm. This protects the appliance from current overload.

Why doesn’t the fuse keep resetting itself?

When the PolySwitch device gets hot, it does not switch off the current
completely as does a melted wire in a fuse. A very small current still flows
through the device. This is enough to keep it hot. Once the fault has been
rectified, the PolySwitch device can be reset by first turning off the power to
allow it to cool.

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Questions
1. Explain the term conjugated.
2. The groups attached to the double bonds in poly(ethyne) can be either cis or
trans. Poly(ethyne) exists in two extreme forms – all cis– and all trans–. Draw
the structure of each. You should draw at least five repeating units.
3. What is the functional group in poly(ethyne)?
4. Why would you expect oxygen to attack poly(ethyne)? Suggest a possible
product of the reaction.
5. Suggest some advantages which a conducting polymer might have over a
conducting metal. Assume that the typical polymer properties are essentially
unchanged (except for electrical conductivity).
6. Draw a displayed formula for poly(pyrrole) showing at least three repeating
units.
7. What is a composite material? What affects its properties?
8. Does the electrical conduction of metals rise or fall as the temperature
increases? (Hint: think about superconductivity.)
9. Look at the formulae of the two polymers below. Predict which one you might
expect to be an intrinsic conductor and explain your choice.

a)

H H H

b) C C C

H H H

Conducting polymers

10. Use a data book to find the bond lengths you would expect for C–C and for
C=C. What is the carbon–carbon distance in benzene? What technique might
you use to find out if poly(ethyne) were in the delocalised or non-delocalised
form?
11. Describe the way in which electrons move in metals and allow them to
conduct electricity. Compare this with the situation in poly(ethyne) and
graphite. Write down any similarities and differences.

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Shape memory polymers information sheet
These polymers ‘remember’ the shape into which they have been moulded and will
return to it on gentle heating.
They are based on thermoplastic polymers. During manufacture the polymer is
moulded into a particular shape and irradiated with β-radiation. It is then heated, re-
shaped and cooled. It does, however, remember the shape which it had when
irradiated and returns to it when re-heated. One application of this effect is heat-
shrinkable sleeves which are used to hold together bundles of wires in car wiring
harnesses (see below).

Applying a shrinkable sleeve

Here a cylindrical length of poly(ethene) sleeve is moulded into shape so that it

has a narrow internal diameter which firmly holds together a bunch of wires. The
sleeve is now irradiated, which causes covalent crosslinks between the poly(ethene)
chains.
The tube is next heated to above its crystalline melting point to soften it. Then it is
stretched into a larger diameter. This stretches the crosslinks. The tube is cooled and
this locks the chains in their stretched position.
Now the large diameter tube can easily be slipped over a bunch of wires. If it is
heated (by a hot air gun or blowlamp) above its crystalline melting point, the
stretched crosslinks pull the material back into the shape it had on irradiation and it
holds the bunch of wires firmly together.

Bonding within polymers

Polymers can be classified as thermoplastic (thermosoftening) or thermosetting.
Thermoplastics soften on heating and can be moulded into a shape which they retain
on cooling. They can be reheated and moulded indefinitely. They consist of long
chain molecules, each chain being essentially independent of the others. There are
no covalent bonds between the chains. The plastics retain their shape when cool
because of intermolecular forces between the chains. In particular there are areas
where the the chains line up in an ordered way – so-called areas of crystallinity. If
crystalline areas on two adjacent chains line up, the intermolecular interactions are
particularly strong. This is responsible for much of the strength of thermoplastics in
the solid state. On heating above the crystalline melting point, increased thermal
motion makes the crystalline areas disappear. The polymer softens, the chains
become free to move past one another and the plastic can be moulded. On cooling,
new crystalline areas re-form, which help retain the new shape (see below).

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 Crystalline areas in a polymer chain

Thermosetting plastics have many covalent crosslinks between the polymer chains
which form as the polymer is made. Once made, the polymer is unaffected by heat
(until it begins to burn or decompose).
Shape memory plastics have a degree of crosslinking (after irradiation) which is
less than that of a thermoset but more than that of a thermosoftening plastic.

Irradiation
How does the irradiation process produce the cross links? β-radiation is a stream of
electrons each with more than enough energy to break covalent bonds. β-irradiation
of poly(ethene) breaks some of the C–H bonds in the poly(ethene) chains. As carbon
and hydrogen atoms have similar electronegativity, the bonds tend to break
homolytically leaving a free hydrogen atom and a carbon free radical, a carbon atom
with a single –ie unpaired – electron. Such carbon atoms are extremely reactive and
two close together may form a covalent bond thus pairing up their electrons. This
forms a crosslink between the chains (see below).

H H H H H H H H H H
β-irradiation
C C C C C C C C C C +H

H H H H H H H H H

H H H H H H H H H H

2 C C C C C C C C C C

H H H H H H H H

H H H H

C C C C C

H H H H H

2H H2

The effect of β-irradiation on poly(ethene)

The hydrogen atoms, which also have an unpaired electron each, tend to come
together to form hydrogen molecules which escape from the polymer.

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Questions
1. What other bonds will the β-radiation break? Suggest what effects this might
have on the polymer.
2. What might happen if too many crosslinks are formed in the polymer? What
effect might this have on its properties?
3. What are the intermolecular forces which operate within the crystalline
regions of a thermosoftening plastic called? Compare the strength of a single
intermolecular interaction with that of a typical covalent bond. Explain why,
when cool, these intermolecular forces have comparable effects to covalent
bonds – ie thermosets and thermoplastics have comparable strengths.
4. Another free radical reaction is that of bromine with methane in ultraviolet
light. The steps are:
1. Br–Br → 2Br•
2. CH4 + Br• → HBr + CH3•
and
Br2 + CH3• → Br• + CH3 Br
UV
3. Br• + Br• → Br2
CH3• + CH3• → C2H6
Br• + CH3• → CH3Br
a) The first step is called initiation. Name the other two.
b) In this case, there are no hydrogen free radicals formed by the
reaction
CH4 → H• + CH3•
Suggest a reason for this.
What does this tell you about the energy of ultraviolet light
compared with that of β-radiation?
c) Which of the three possibilities for step 3 above is most similar to
the reaction which occurs in the polymer crosslinking reaction?
Explain your choice.
5. Explain the terms homolytically and electronegativity as used in the passage.

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