ChE EL 10

5. Structure-Property Relations

Other Properties of Polymers

ELECTRIC MEASUREMENTS

1. Dielectric constant

2. Electrical resistance

3. Dissipation factor and power factor

4. Arc resistance

5. Dielectric strength

Dielectric Constant — Dielectric constant is the ratio of the capacity of a condenser made
with or containing the test material to the capacity of the same condenser with air as the
dielectric.

Insulators in electrical applications should have low dielectric constants

Conductors or semiconductors should exhibit high dielectric constants.

Electrical Resistance — There are a number of electrical properties related to electrical

resistance. These include:

a. insulation resistance

b. volume resistivity

c. surface resistivity

d. volume resistance, and,

e. surface resistance.

Conductive materials, such as copper, have specific resistance values of about 106 ohm cm,
whereas good insulators, such as polytetrafluoroethylene (PTFE) and low-density
polyethylene (LDPE), have values of about 1017 ohm cm.

Dissipation Factor and Power Factor — The dissipation factor can be defined as the ratio
of the conductance of a capacitor (in which the material is the dielectric) to its susceptibility.
Both the dielectric constant and dissipation factor are measured by comparison or
substitution in a classical electric bridge. The power factor is the energy required for the
rotation of the dipoles of a polymer in an applied electrostatic field of increasing frequency.
These values, which typically range from 1.5 ╳ 104 for polystyrene to 5 ╳ 102 for plasticized
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cellulose acetate, increase at Tg because of increased chain mobility. The loss factor is the
product of the power factor and the dielectric constant, and is a measure of the total electric
loss in a dielectric material.

Arc Resistance — a measure of the resistance of a material to the action of an arc of high
voltage and low current close to the surface of the sample to form a conducting path on this
surface. Arc resistance values are of use in surface quality control since small surface
changes will affect the arc resistance value.

Dielectric Strength — The insulating property of materials breaks down in strong fields.
This breakdown strength is called the electric or dielectric strength (DS), i.e., the voltage
required for failure. Breakdown means sudden passage of excessive current through the
material, which often results in visible damage to the specimen. The DS is high for many
insulating polymers and may be as high as 103 MV/m.

WEATHERABILITY

Polymers are used in almost every conceivable environment.

They are tested for their interactions with:

- radiation,
- weather, and
- microorganisms.
Weathering includes the ability to resist attacks by

- freezing and heating cycles,

- resistance to frictional damage caused by rain and air, and
- influence of high and low temperatures as the polymeric material is used.
Accelerated Tests — Since tests are expensive and time consuming, accelerated tests have
been developed in an attempt to gain “accelerated” test results. Some of these tests
include:
- exposure to light
- selection of light source
- cyclic exposure to varying degrees of humidity.
- other accelerated tests include salt spray, heat, cold, and other weather factors.
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Environmental stress cracking (ESCR) test can also give a measure of weatherability.

Resistance to moisture — Moisture is an important factor for some polymers, especially

condensation polymers where hydrolysis, and subsequent degradation, can bring about
drastic changes in chain length. Such attack can occur on the surface and is indicated, as
can many chemical attacks, by a discoloration generally followed by crazing and cracking.

Nonpolar polymers such as polyethylene have low water absorption whereas more polar
polymers such as polycarbonates, nylons, and polysaccharides have relatively greater
moisture retention.

Resistance to biological attack — important for many polymer applications including almost
all of the biomedical applications, food storage and protection, and coatings where
microorganism destruction is important.
- Most synthetic polymers are resistant to destruction by microorganisms. This is
particularly true for nonpolar polymers, but less so for condensation polymers such as
nylons and polyesters.
- Preservatives and antimicroorganism additives may be added, when appropriate, to
protect the material against these microorganisms.

OPTICAL PROPERTY

Important since polymers are often used as clear plastics or coatings and have many
applications in which transparency is an important property.

Most polymers are transparent and colorless, but some, such as phenolic resins and
polyacetylenes, are colored, translucent, or opaque.

Clarity is typical for light passing through a homogeneous material, such as a crystalline
ordered polymer or a completely amorphous polymer.

Interference occurs when the light beam passes through a heterogeneous material such as
a polymer containing both crystalline and amorphous regions.

Polymers that are transparent to visible light may be colored by the addition of colorants,
and some become opaque as the result of the presence of additives such as fillers,
stabilizers, flame retardants, moisture, and gases.

CHEMICAL RESISTANCE

In general,
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- Condensation polymers, because of the polarity of the connective “condensation”
linkages within the polymer backbone, have good stability to nonpolar liquids and are
(relatively) moderately or unstable toward polar agents and acids and bases.
- Vinyl type of polymers exhibit moderate to good stability toward both polar and nonpolar
liquids and acids and bases. This is because the carbon–carbon backbone is not
particularly susceptible to attack by polar agents, and nonpolar liquids, at best, will simply
solubilize the polymer.
- The materials in the table below show good stability to water because all of the polymers
have sufficient hydrophobic character to repeal the water.

STABILITY OF VARIOUS POLYMERS TO VARIOUS CONDITIONS

THERMAL STABILITY/DEGRADATION

Routes of thermal degradation:

1. Chain scission:

(a) random degradation — chain is broken at random sites

• results to complex mixture of low-molecular-weight degradation products.

• e.g. PE and PP

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• in the case of 1,1-disubstituted vinyl polymers, the radical segments formed from
the initial scission reaction will depolymerize

(b) depolymerization — monomer units are released from an active chain end

(c) weak-link degradation — chain breaks at the lowest energy bonds

2. Non-chain scission reactions — example: dehydrogenation, which results from the

breakage of a carbon-halogen bond and the subsequent liberation of hydrogen halide.

Strategy for Thermally Stable Polymers

- flame-retardant additives
- comonomer designed to improve the fire resistance of certain polymers
- highly aromatic structures show thermal stability for extended periods of time. However,
they have high Tg, high melt viscosity, and insolubility in common organic solvents make
them difficult to process.

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CEILING TEMPERATURES OF SOME COMMON VINYL POLYMERS (SOURCE: POLYMER SCIENCE

AND TECHNOLOGY, 3RD EDITION. PRENTICE HALL)

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EXAMPLES OF THERMALLY STABLE POLYMERS (SOURCE: POLYMER SCIENCE AND TECHNOLOGY,
3RD EDITION. PRENTICE HALL)

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