PHYSICO-CHEMICAL

PROPERTIES OF NYLONS

L. Costa e P. Bracco
University of Torino

How a polymer chain is structured?

. Which is its chemical structure?

. How long is it?
. How polymeric chains are organised in the rope?
. How do mechanical properties vary?
. Why polymers can degrade?

Chemical structure:

Nylon 6 o PA-6

Caprolactam

H2N

amino caproic acid

(CH2 )5

( NH

COOH + H2N

(CH2 )5

CO

Poly(caprolactam)

)n

(CH2 )5
H 2O

COOH

Chemical structure:

Nylon 6,6 o PA-66

Hexamethylene diamine + Adipic acid

H2N

( NH

(CH2 )6

(CH2 )6

NH2

NH

+ HOOC

CO

(CH2 )4

(CH2 )4

CO

)n

COOH

+ H 2O

Chemical structure:

(
( NH

NH

(CH2 )5

(CH2 )6

NH

CO

Nylon 6

)n

CO

(CH2 )4

CO

)n

Nylon 6,6

Same C/H/N/O ratio, but different structures: they are

different materials with different physico-chemical and
mechanical properties

How long a nylon chain is?

Two definitions:
n = polymerisation degree (number of monomeric
units into a polymer chain).

( NH

(CH2 )5

CO

)n

For nylon fibres ca. 150 units

Molecular mass
Can we define a scale model?

Rope:
10,5 mm,
length 7-8 m.

Amorphous
phase

Crystalline phase

Which are the differences between crystalline and

amorphous phases?
Crystalline phase
Nylon 6 crystal
obtained from a 1-4
butanediol solution
Melting temperature
of the crystalline
phase:
Nylon 6

225C

Nylon 6,6

265C

Nylon 6 crystal form

Nylon 6,6 crystal form

Fibres are obtained by

drawing.
The chains are oriented.
Which percent of
nylon is crystalline
phase and which
amorphous phase?

50% of crystalline
phase

tg.dir

What happens during molten nylon cooling?

At the crystallisation temperature, only part of the

polymer chains will organise into crystalline structures,
while some will remain in the molten state, below the
melting temperature, with a high mobility. A further
temperature decrease, will drive to a temperature in
which the chains will tie as in the solid state.

Glasses (Polystyrene):
Tg 100C

Rubber: Tg -40C

Bottle (LDPE): Tg -70C

The transition temperature between the rubbery liquid

state and the glassy solid state is named glass transition
temperature (Tg)
At this temperature the mechanical properties of the
polymers undergo dramatic changes

Which is the Tg of nylons?

Dry:
Nylon 6

circa 60C

Nylon 6,6

circa 80C

decreasing in humid atmosphere.

Any other difference between amorphous and

crystalline phase?

In the amorphous phase the chains are more spaced and

small molecules (i.e. water, oxygen) can penetrate into the
polymer, moving through the voids (diffusion process).

Do polymers degrade upon time?

Thus, can the physico-chemical and mechanical
properties of polymers decay upon time?

YES
50-80

Grandezza fisica
Grado di polimerizzazione

The most relevant degradation is a

decrease of the polymerisation degree

If the original polymerisation degree was 150,

2 bond scissions will give chains of 50 units.

Two main processes:

Hydrolytic degradation: due to the action of water.

Can be excluded in the conditions of use of a rope.

Photo-oxidative degradation: the combined effects of light

and oxygen can lead to chain scissions.

The UV radiation (especially with wavelengths below 290

nm) has enough energy for breaking bonds omolitically,
giving very reactive radicals.

The radicals react with oxygen starting a

cyclic process.

O2 by air

Reaction 1

CH2

CH

CH2

CH2

CH

CH2

O O
Reaction 2
CH2
CH2

CH
O

CH2

CH2

CH2
OH

Reaction 3
ketones, alcohols, esters and carboxylic acids

If you wish to know more about the polymers, try

polymers on the web:
http://www.psrc.usm.edu/macrog/index.htm

http://www.polial.polito.it/cdc
Reference:
Nylon Plastics Handbook ed. Melvin L. Kohan
Hanser Publishers Munich

Thank you