Formation of Fibre Structure

 Formation of molecular orientation and crystalline plays an important role in

melt spinning and thus affects the ultimate structure and physical properties of
fibers. Figure describes a typical fiber structure formation process in melt
spinning.
 Molecular orientation arises from parallelization of the molecular chains along
the fiber axis in both the crystalline and non-crystalline regions.
 During melt spinning, the molecular orientation develops in two stages: in
spinneret channel and under elongation.
 Molecular alignment is developed when the polymer melt is forced through a
capillary channel.
 As it comes out of the spinneret, the molecular alignment becomes
disorientated and thus contributes very little to the final fiber orientation.
 The major contribution of orientation is made by the elongational flow along
the spinline.
 The parallel velocity gradient, the relaxation time distribution and the elapsed
time are the important factors which affect the molecular orientation.
 For example, a higher heat transfer coefficient results in an increase in orientation
since it causes more effective freezing of orientation on filament quenching.
 The molecular orientation also increases with the increase in takeup speed,
extrudate viscosity and reciprocal of polymer mass flow rate.
Kinematics of Melt
Spinning
 The velocity distribution and profile of the polymer melt appear in different
forms along the spinline, which play an important role in the fiber formation.
Inside the spinneret channel, the polymer flow is a typical flow with a
parabolic velocity profile.
 By assuming an incompressible Newtonian liquid of viscosity η through a
capillary of radius R and length L, the radial velocity distribution can be
described as:


 where P is the pressure difference between the inlet and outlet of capillary.
 The velocity profiles

(a) shear flow in a capillary (b) elongational flow in a spinline

 Figure shows the differences on velocity profile

between shear flow and elongational flow.
 When polymer is extruded out the orifice, a phenomenon of die swell is
observed due to the relaxation of stored elastic energy.
 The degree of swelling depends on the conditions of extrusion,
temperature and geometry of the die.
 For example, in melt spinning, the die swell ratio decreases with the
increase of extrusion temperature.
 Under take up tension, the flow of polymer melt transits from shear flow to
elongational flow, or uniaxial extensional flow.
 In elongational flow, the velocity keeps increasing along the spinline and
finally reaches the take-up speed.
Melt Spinning Variables and Conditions
for Continuous Spinning** (Assignment)
 Melt Spinning Variables
 There are many variables that determine the course of fibre formation and
fibre dimensions and Properties.
 Ziabicki Divided these into three groups:
 Independent or Primary Variables, which ultimately determine the course of
spinning process and the resulting fibre structure and properties.
 Secondary Variables: which are related to Primary Variables through the
Simple geometrical relationships and are useful in defining spinning
conditions.
 Resulting Variables: Which are determined by independent variables through
the fundamental laws of spinning kinetics.
These groups are further subdivided as
follows:
1. Independent (primary) variables;
 (a) Polymer materials;
 (b) Extrusion Temperature (To);
 (c) Spinneret Channel Dimensions (do, diameter and lo, length )
 (d) Number of filaments in spinning line (n)
 (e) Mass Output rate (W)
 (f) Spinning Path length (L)
 (g) Take up velocity (VL)
 (h) Cooling conditions (cooling medium, its temperature and flow rate)
2. Secondary variables:
 (a) Average extrusion velocity

 (b) Equivalent diameter of single filament at x=L;

3. Resulting Variables:
 Flow Instablities

 One of the primary concerns of the fibre industry is to produce filaments with
uniform diameter or cross-section.
 Flow instabilities can introduce non-uniformities and are therefore to be
avoided.
 The main instabilities are arise during fibre spinning can be considered under
two headings;
 The First has its origin in the spinneret channel- the two instabilities under
this category are die-swell and melt fracture.
 The Second type of flow instability occurs when the spin draw ratio reaches a
critical value and is termed as draw resonance.
Die Swell and Melt fracture

 Die Swell appears as bulge in the extruded filament at the spinneret exit.
 Melt fracture refers to distortion of extrudate surface; while the severity
ranging from simple roughness to helical indentations.
 Both these flow stabilities are believed to result mainly from the elastic
energy stored in the viscoelastic fluid during the passage through the
spinneret orifice.
 If the relaxation rate of fluid molecules is fast, significant relaxation of
stored elastic energy can take places.
 Die-Swell
As the polymer is pushed through a spinneret hole under pressure, some energy is
utilized in the flow of the fluid but part of the energy is stored as elastic energy.

When the polymer comes out on the other end, this stored energy is released
and the polymer fluid relaxes to give a swelling of the extruded fluid jet.

Extrudate swell is measured as the ratio of diameter of the swollen

extrudate/diameter of the spinneret.
High extrudate swell results in improper flow or spinning of the material in the
spinning line and therefore must be minimized.

It may also result in fusing of filaments if the spinneret holes are placed very
close to each other.

In order to reduce the extrudate swell, the flow conditions must be controlled in
such a way so as to control the elastic character of the polymer fluid.
On what factors does the extrudate
swell depend?

The extent of swelling would depend upon the amount of energy stored in the
polymer during its travel through the spinneret cylinder.

The factors that would make the polymer more elastic would result in the higher storage of
elastic energy, and therefore, give higher extrudate swell on extrusion.

A fluid shows elasticity, as mentioned earlier, because of its inability to dissipate stored
energy through chain relaxation. Therefore, if the relaxation time of the polymer is
reduced, extrudate swell also reduces. This can be achieved by increasing the
temperature of spinning melt, lowering molecular weight of the spinning polymer, adding
plasticizers or other additives in the polymer fluid.
 Alternately, the polymer may be provided more time inside the spinneret, so
that it has sufficient time to release the stored energy before the extrusion.
 Therefore, dimension of the spinneret have a big role to play in reducing the
extrudate swell. Higher L/D ratio for a given spinneret diameter is beneficial
in reducing this instability.
 When polymers with extremely high molecular weights are spun, such as, high
molecular weight polyesters or HDPE for high performance fibres, the L/D
ratios of the spinneret holes are kept high to allow the polymeric fluid enough
time to release stored elastic energy.
 Polydispersity index (PDI), known as molecular weight distribution, also has
a significant effect on extrudate swell.
 Extrudate swell has been found to increase with increasing PDI for a series
of linear low density polyethylene polymers with same molecular weight.
 On the other hand, extrudate swell can also be reduced by reducing the
rate of fluid deformation. Higher shear rates would result in higher storage of
energy per unit time, and would cause a higher extrudate swell ratio. Shear
rates may be lowered by either decreasing the flow rate for the given
spinneret or increasing the diameter of the spinneret capillary for the given
flow rate.
 Melt fracture
 Melt fracture is indicated by distortions of the extruded filament. It is visible on the
surface of the filament as irregularities.
 As the name suggests, melt fracture is fracture of the molten material as it flows
through the spinneret into the spinning space.
 It happens because of the inability of the polymer melt to stay together as a
continuous fluid at a high shear rate.
 At any given temperature, polymer network has certain degree of mobility and it can
move only at shear rates lower than a critical value known as critical shear rate.
 If the polymer is made to flow at a shear rate higher than the critical value, it is
unable to keep the continuum and moves in a discontinuous flow. Since the shear
rates are highest at walls of the capillary, the first signs of fracture appear at the
surface of the extruding filament in the form of distortions.
 What are the factors on which melt
fracture depend?
The value of critical shear rate for the melt fracture of a polymer depends on its ability to
move at a given set of conditions. The faster a polymer network is able to relax, the higher
is its value of critical shear rate at those conditions.

The relaxation time of the polymer decreases with the following parameters:

• Increasing temperature of flow

• Decreasing molecular weight and its distribution
• Presence of plasticizers or additives

The shear rates for onset of melt fracture are strongly dependent on molecular weight.
 During spinning, melt fracture occurs, if the polymer is made to flow at a flow
rate that would create shear rates higher than its critical value in a given
spinneret at a given spinning temperature.
 Melt fracture, may also occur near the exit of the spinneret plate because
the face of the spinneret plate tends to have a lower temperature due to its
exposure to a cooling quench zone just below it.
 Since the critical shear rate of a polymer depends on the temperature at
which it is flowing, the lower temperature may cause melt fracture to
happen at that position.
 To avoid melt fracture at the exit portion of the spinneret plate, a heater band
may be used just below the spinneret to avoid cooling of the spinneret
plate surface.
Dependence of critical shear
Typical fractured extrudate
rate on polydispersity index
appearances of polymers
(PDI)
What is draw resonance?

 Draw resonance occurs in the extensional flow region of the spinning line after the
extrusion of the filament.
 Draw resonance is the periodic fluctuation of the filament diameter at the take up of
the spinning line.
 Draw resonance manifests itself at a critical draw ratio by the occurrence of
sustained periodic oscillations in spin-line variables such as filament cross-section
and tension despite maintaining constant extrusion rate and take-up velocity.
 It can be recorded as a systematic deviation from unity in the ratio of maximum to
minimum diameter of the drawn filament with increasing draw ratio.
 Draw resonance is an undesirable behavior of polymer fluids which affects the
stability of polymer processing. Avoiding draw resonance or draw resonance induced
spin breaks is essential in producing continuous fibres having uniform thickness and
properties.