Heatsetting

Heat-setting or annealing of the drawn fibres is an important post spinning operation. It is carried out to bring the
material to its thermal equilibrium at a particular temperature of use. At thermal equilibrium, the material would not
change its morphology even if kept at that temperature for a long time.

The degree of set, a term often used to describe the extent of heat setting is the measure of how close the material has
moved to a thermal equilibrium. A 100% set material is considered to be at its thermal equilibrium at a given
temperature.

Types of heat-setting

There are three types of heat-setting:

(a) temporary heat setting

This type of setting is destroyed with regular use of the materials. For example, a steam pressed cotton textile.

(b) semi permanent heat setting;

In this type of heat setting, material is raised above its Tg and then set into a new form. This type of set is maintained
with normal use of the material, however, the setting is lost when the material is subjected to severe conditions of
use.For example, hot washing or steaming of material above Tg.

(c) Permanent heat setting. This type of heat setting involves change of internal morphology of the material in such a
way that it would not reverse till the material is destroyed by taking it above its melting point.

For example: Heat setting to develop new crystallites. In this form the crystals can only be destroyed by heating the
material above its melting point. This would destroy the fibre itself, and therefore, such conditions of high temperature
can not be given under normal use.

Parameters of heat setting

The permanent heat setting is the most important of the three types described above as this can be used to stabilize the
material in its final form. As the spun yarn is drawn during a drawing operation, it undergoes chain orientation and
crystallization under stress. This leaves the material with a lot of internal stresses and incomplete crystallization
process. If left like this, the drawn yarns would tend to shrink slowly depending upon the temperature of use and start
to lose their orientation. Also, they may continue to crystallize with time and assume an undesirable form. These
materials can be brought to thermal equilibrium by heat treating them (i.e. annealing them or heat setting them) at the
temperature of crystallization for a short time. This releases their internal stresses and helps in development of more
crystals that can lock the structure in the oriented state.

There are several parameters that can affect heat-setting. These are as follows:

(a) Temperature of heat setting

Heat-setting involves formation of new crystallites in the amorphous part of the fibre. The formation of crystals is a
thermal process and maximizes at a certain temperature. Crystallization involves nucleation followed by growth of the
nucleated crystallite. Nucleation is facilitated at a low temperature, while growth is facilitated at a higher temperature.
Since rate of crystallization involves both nucleation and growth. There exists an optimum temperature for a given
fibre, where the rates of nucleation and growth together result in the highest rate of crystallization.

The rate of crystallization is also dependent on the orientation of the fibre being crystallized. At higher orientation, the
rates of crystallization may be significantly higher than the lesser oriented material. Therefore a drawn yarn may
undergo heat-setting through crystallization in a fraction of time than otherwise needed for an unoriented yarn.

Temperature of heat-setting also has another effect. At a high temperature, oriented chains tend to relax fast and fibre
can lose its orientation if left at that temperature for a sufficiently long time. Therefore there is a competition between
the relaxation of polymer chains resulting in shrinkage of the fibre and locking of structure due to formation of
crystallites.

Therefore, selection of an appropriate temperature for heat-setting is very important so that thermal equilibrium may
be reached without significantly losing the orientation.

(b) Time of heat setting

As explained above, the rate of crystallization is dependent on the temperature of heat setting and the orientation of the
drawn yarn. Also, the disorientation is a function of time. Keeping in view the two, the time is decided so that thermal
equilibrium is reached in a minimum time with minimum loss of the orientation.
(c) Tension given to the material during heat-setting:

The drawn yarn may be subjected to heat either in loose (free) or taut (stretched under tension) form. In free form, the
chains can disorient at a faster rate and fold to form lamellar crystals at the heat setting temperature. This results in
high shrinkage of the fibres and lowers connectivity among the polymeric chains ( Figure 4.13 ). Though the yarn
reaches thermal equilibrium easily (i.e. 100% set), it loses all its mechanical properties. Because the connectivity
(network formation) is poor among the chains, the fibres are unable to elongate (low extensibility) and bear load (low
strength).

Figure 4.13: Heat setting of drawn yarn in free and taut form.

Applying tension at the time of heat-setting restricts the rate of folding of polymeric chains, which gives enough time
for small crystallites to grow along the length of oriented chains. This improves connectivity among the oriented
chains as many chains are involves in a single crystallite ( Figure 4.13 ). However, the polymer chains have difficulty
in reaching thermal equilibrium and heat-setting may remain at levels lower than 100%.

Heat-setting under tension is able to retain mechanical properties of the starting material. When high values of tension
are applied, even marginal improvement of tensile strength may be achieved.
(d) Moisture in the starting material and its sensitivity to it

Certain polymers such as nylons are sensitive to moisture. Their Tg becomes lower as their moisture content increases.
Since moisture acts as a plasticizer for such materials, their chains may relax and fold easily when in wet state
compared to the dry state.

For example, in drawn nylon 6, the dye uptake and the diffusion coefficient are generally increased when heat-setting
is carried out by steam. This tendency increases with the temperature of the steam setting. However, dry heat setting
up to about 160C gives the reverse tendency. With steam, chains fold to grow into large crystals and the molecular
packing of amorphous regions loosens as a result of inclusion of water.

On the other hand, in dry heat setting, the increase in crystallinity and also closeness of packing in the amorphous
regions results in poor dyeability and diffusion coefficient of the heat-set material.

Interestingly, in both types of setting treatments, the diffusion coefficient decreases with increasing tension of the
sample during heat-setting.

(e) Morphology of starting material

The morphology of the starting material has significant effect on the effectiveness of the heat-setting process. If a
material is already crystalline, it may not undergo setting to retain a deformed state.

Therefore, materials which have tendency to crystallize during spinning or during storage such as nylon and
poly(propylene) are difficult to heat-set. In such materials, imperfect crystallites such as pseudo-hexagonal (higher
energy crystalline) phases in nylon-6 or smectic crystallites in poly(propylene) may undergo transformation into
perfect monoclinic phase on set-setting. However, phase of nylon-6 induced during high speed spinning of nylon-6
has been found to be extremely stable to heat and does not convert to phase even with high temperature annealing.

Effect of heat-setting on morphology of fibre

As explained earlier, heat-setting involves bringing the material to its thermal equilibrium. This is achieved when a
material, which has a tendency to crystallize can crystallize to the maximum extent possible with the given structure. A
polymeric material owning to its entanglements and defects can never achieve 100% crystallinity or even close to it.
As the crystals develop, entanglements and defects are thrown out to the remaining amorphous regions. With this it
becomes increasing difficult for the remaining amorphous regions to convert to ordered crystalline regions. As
crystallization proceeds, a time comes when further conversion of amorphous region to crystalline region results in
increasing the overall energy of the system, the conversion stops and a thermal equilibrium is reached.

Annealing can increase crystallinity of the material, transform imperfect crystals into perfect low energy form of
crystals, grow smaller crystals into larger crystals. Also, long range order, such as fibrillar structure of the fibres, may
also change with annealing. All such changes are dependent on the parameters of heat setting used in the process. For
example, long range order of nylon-6 undergoes marked increase with steam-setting in comparison to dry-heat-setting
(Figure 4.14 ).

Figure 4.14: Effect of heat

setting conditions on long
range order of heat set fibres

Morphology of a fibre can also be explained by a modified Tagayanaki Model proposed by V. B. Gupta. In this model,
shown in Figure 4.15 , the crystalline regions of a fibre are connected (coupled) in series as well as in parallel with the
amorphous region. These values are shown by and fractions, respectively.
 Figure 4.15: Representation of
modified Tagayanaki model

If increases to 1, then the entire crystalline region gets coupled with amorphous region in series and if factor
becomes 1, then the crystalline region gets coupled in parallel with the amorphous region. With heat-setting, these
parameters tend to change as shown in Figure 4.16 . As shown in the figure, with free annealing, the fraction of series
coupling increases, while that of parallel coupling reduces significantly. Whereas, on taut annealing, though series
coupling still increases, the drop in parallel coupling is significantly less.

Figure 4.16: Effect of degree

of heat setting on parallel ( )
and series ( ) coupling for
free and taut annealing