Man Made Fibere
Man Made Fibere
Man Made Fibere
Core-sheath
Side by side
In addition to these main classes, a wide variety of bicomponent fibres having different cross-sectional
geometries can be produced.
Typical Applications:
The bicomponent fibres can have a range of functionality and find applications for different end-uses as given
in Table 1.
Table 1. End-Use Applications of Bicomponent Fibres depending upon different functionalities
Functionailty Some End-use Applications
Antistatic Lining clothes,workwear,knitted fabrics,underwears
Liquid absorbing Sports wear,felt pens,liquid absorbers,underwears
Self-crimping Stockings,beddings,heat insulators,knitted fabrics,carpets
Thermal Bonding Nonwoven fabrics,beddings,mattresses, printing screens,cushions,
Electro-conductive Carpets,seatings,workwear,kinitted fabrics
Light-conductive Communication,decoration,telephone
Enhancement of properties such as - mechanical properties,
Other
aesthetics,dyeability,water repellency,flame retardancy
The first commercial bicomponent fibre was introduced by DuPont in the mid 1960s. This was a side-by-side
hosiery yarn called "cantrese" and was made from two nylon polymers, which, on retraction, formed a highly
coiled elastic fibre. In the 1970s, various bicomponent fibres began to be made in Asia, notably in Japan. Very
complex and expensive spin packs were used for manufacturing. These techniques were found to be technically
unsatisfactory and excessively expensive. Later in 1989, a novel approach was developed using thin flat plates
with holes and grooves to route the polymers. This process was very flexible and quite price effective.
These are melt-spun in a specially designed spinning manifold. Separate extruders and metering pumps are
used for both components. Ratio of the polymers can be controlled by varying the speed of the metering pumps.
In core sheath structure, one of the components called core is fully surrounded by the second component known
as sheath. In this configuration, different polymers can be applied as a sheath over a solid core of another
polymer, thus resulting in variety of modified properties while maintaining the major fibre properties.
Figure 3. Different types of bicomponent fibres a)-d)Coresheath, e) Eccentric core-sheath and
f)Multiple core-sheath
Concentricity/eccentricity of the core can be tuned according to end application. If the product strength is the
major concern, concentric bicomponent fibres are used; if bulkiness is required at the expense of strength, the
eccentric type of the fibre is used.
These fibres can be useful for applications where
Core imparts strength (reinforcing material) and sheath has dyeability, soil resistance, heat-insulating,
and adhesion properties. Some examples include:
o bonding fibres used in carpets, upholstery etc., where the sheath is made of PE and core is made
of high melting point material like nylon.
o antisoil-antistatic fibres, made using a PET-PEG block copolymer containing polyester core
Sheath can be made from expensive material to increase visual appearance. And the core can be of low
cost material to control cost.
For making self crimping fibres. Crimp can be controlled by changing the eccentricity. Eccentricity of core
can be varied to balance strength and bulkiness: used in pillows and furniture.
In a simple technique to produce core sheath fibres, the two polymer liquids are separately led to a position
very close to the spinneret orifices and then extruded in a core sheath form as shown in Figure 4.
Figure 4. Technique for Core-Sheath Fibre formation
In case of concentric fibres the core polymer is in the centre of the spinning orifice outlet and flow of the core
polymer fluid is strictly controlled to maintain the concentricity of both components, while eccentric fibre
production is based on following approaches:
eccentric positioning of the inner polymer channel and controlling of the supply rates of the two
component polymers
introducing a stream of single component merging with concentric sheath-core component just before
emerging from the orifice
deformation of spun concentric fibre by passing it over a hot edge
coating of spun fibre by passing through another polymer solution
spinning of core polymer into a coagulation bath containing aqueous latex of another polymer
These are made from alternate wedges made from two different polymers. The number of wedges is around 16
to 32 and the spinning manifold is complicated. The fibre is drawn to high draw ratio and sometimes splitting
may occur while drawing.
The splitting is carried out by partial or complete dissolution of one component. Fibres obtained are of fine
denier and sharp cross section.
These are used for making non-woven web with ultra fine fibres. The resultant fabric is stronger and has higher
surface area.
Figure 8. Segmented pie bicomponent fibres
Figure 11. Radial petal like conjugate fibres: (a) without central hole and (b) with central hole
Islands in the sea
These are also called as matrix-fibril fibres. In cross section there are areas of a polymer (island) in the matrix
of the other (sea).
Figure 12. Schematic showing melt spinning of islands in sea fibres
These are also used to produce finer fibres. Sheath is made up of a dissolvable material and core is made up of
desired material. Sheath is dissolved in proper solvent giving micro denier fibres.
the presence of pristine and carboxylated multi-walled carbon nanotubes (MWNT and MWNTCOOH), both the storage modulus
(E') and glass transition temp. (T ) of the PA6/CNTs composites have been found to increase significantly.
g
These drawbacks can be overcome by changing processing conditions or molecular weight, introducing additives or fillers to
polymer matrix, or by copolymerization with new monomers. Incorporation of third/or fourth component or nano materials into
PET backbone during polymerization changes some of the fundamental properties of the polymer. Production of PET
copolymers for textile applications is certainly not new and a brief summary is given in Table 1.4 below.
Table 1.4: Various approaches for modification of Polyester.
Type of Modified
Approach By using
PET
By Reducing T using a
g Segments of polyethylene oxide
Deep dyeable PET
flexible comonomer (PEO) in PET backbone
Carrier free By adding additives that reduce polyethylene glycol ( PEG), adipic
dyeable PET the T g acid to form block copolymers
Cationic dyeable By introducing sulphonic acid 5-sulpho-isophthalic acid as
PET groups comonomer
By copolymerizing with
Biodegradable Tetra methylene succinate or
polyethers or aliphatic
PET ethylene succinate copolymers
polyesters
Flame retardant By introducing phosphorus phosphate esters for
PET containing groups copolymerization
By block copolymerization
Antistatic and introduction of polyethylene oxide
with hydrophilic, humectant
antisoiling PET by block copolymerization
polymer
Replacement of some Dimethyl-2,6-
High performance
phenylene units by more rigid naphthalenedicarboxylate for
PET
aromatic units copolymerization
Introduction and melt spinning line
What is a fibre?
A fibre or a filament (a continuous form of fibre) is the fundamental unit of textile materials. It has high strength (tensile, bending,
torsional, or compression), high flexibility (i.e. low moduli), extensibility, and shows recoverability on deformation. Most of these
properties are observed about one principal direction, which is known as the axis of the fibre. Since all textile structures -one to three
dimensional (yarn, fabric, or braids etc.), are built using this basic structural unit, these structures also possess such unique properties.
In order to possess such properties, the fibre or filament has a unique micro structure (morphology) in which majority of the polymer
chains are oriented in the direction of the axis of the fibre. The more oriented the polymer molecules are in this direction, the better
properties the resulting fibre/filament is considered to have.
How are fibres made?
Nature has its own ways of arranging these polymer chains in unidirectional orientation to make natural fibres such as cotton, jute and
wool, etc. This process possibly involves constructing the natural polymers, such as cellulose and proteins, bond by bond while it is
being simultaneously organized in an oriented form. Spiders and silk worm also have a unique methodology of spinning, where the
hydrophilic parts of different polymer chains are forced to come together in an oriented form inside the duct of the insect. As this
material is extruded, stretched and dried outside the insects body, it converts into a stable, water insoluble highly oriented structure.
However, at present, we are unable to adopt such methodologies for producing man-made fibres/filaments. For producing man-made
fibres, the polymers (either natural or synthetic) must be unfolded and extended uni-directionally to extremely large dimension to get
high aspect (length to diameter) ratio and high orientation. This is known as spinning.
In spinning, a small amount of polymer (say ~1 g) may be elongated to over 9000 km of length while the other dimension (diameter) is
only in microns. This requires a precise control over the spinning process to enable such unidirectional extensions in melt form. In fibre
formation, all efforts are directed in controlling the microstructure of the polymer so that properties as mentioned above are obtained
with respect to the principal axis of the fibre. This is unlike other methods of polymer processing such as injection molding,
compression molding, extrusion and blowing etc., where mostly isotropic properties are desired and only a little attention is directed in
making a controlled microstructure in terms of molecular orientation and their spatial arrangement. The engineering complexity of the
spinning operation is evident from the fact that, in modern spinning plants, large amount of polymer is expected to be continuously
converted (spun) into filaments without any breaks.
FIBER SPINNING CONCEPT
What is involved in the process of spinning?
In a typical spinning process, polymer melt or solution is extruded from a fine hole and is elongated by applying a tensile external force
on the extruded portion. As the polymer melt or solution is pulled, it is cooled or precipitated, respectively, to form a solid filament. This
filament is then usually subjected to post spinning operations such as drawing, which is unidirectional stretching in a semi solid form,
and heat-setting, which is crystallization to equilibrium. Other post spinning processes such as texturing is simply a variation of the
drawing and heat-setting processes to impart curvilinear shape to an otherwise straight filament. This gives physical bulk to the
filaments. The process of fibre formation is complete only when both spinning and post spinning operations are carried out. In this
module, an attempt has been made to present the fundamental principles involved in fibre formation.
What is melt spinning?
Melt spinning is a process for producing filaments. However, only those polymers that can be melted without undergoing thermal
degradation can be spun into fibres/filaments using this process. Some of the typical examples are nylon-6, nylon 66, poly(ethylene
terephthalate) and poly(propylene). Though, melting is the essential criteria for carrying out melt spinning, it is not the sufficient
condition. There are other requirements that a polymer should meet before it can be regarded as spinnable. These are discussed in
detail later in this section.
What are the various components of a melt spinning line?
A typical melt spinning setup consists of a melting device-normally an extruder, a manifold- distribution arrangement for the melt, a
metering pump- device to regulate polymer flow rate, a spin-pack- arrangement to filter and extrude the polymer through fine holes, a
quench duct- cooling zone for the extruded polymer filament to turn solid, and a winder- a device to pull and wind the solidified
filament. This arrangement is shown schematically in Figure 2.1 . The entire line from extruder output to the spin pack are maintained
at a constant temperature, which is called the spinning temperature.
Figure 2.1: Schematic diagram of melt spinning machine
Each of these components in the spinning process has a critical function to perform, which will become clear as the discussion
continues. The polymer is taken in chip form, which is a cylindrical form having dimensions in the range of 1-3 mm. A polymer chip is
first subjected to an extruder.
1.What is an extruder and what does it do?
In earlier days, the polymer chips were melted using heating grids, however, now, extruders have completely replaced other melting
arrangements. Even when polymer is fed to spinning section in melted form directly from a continuous polymerization line, the extruder
is often used as the first device in the spinning line. This is because an extruder performs multiple functions. Apart from melting solid
polymer chips, an extruder homogenizes the melt by mixing it at various stages. Homogenization is an important aspect in order to
ensure continuous spinning without any breaks or non-uniformity in the spun yarns.
Extruder compresses the polymer fluid to remove any trapped gasses including air/nitrogen that is drawn along with the chips as they
enter the extruder. It also helps in metering the flow rate in the spinning line. It is the first control of flow rate. Finally it acts as a
polymer fluid pump and provides the necessary pressure that is required by the polymer to flow from the extruder to the metering
pump.
What is the design of the extruder?
In order for the extruder to carry out all these functions effectively, extruder design is very critical. Figure 2.2 shows the schematic
diagram of a typical extruder. It has a cooled feeding zone- where the chips enter the extruder, a melting zone- where chips melt with
the heat supplied by the heaters and the heat generated by the dissipation of the polymeric viscous forces, a compression zone-
where the material is compressed into a smaller volume to push out trapped gasses. This is followed by a metering zone, which is the
narrowest part of the extruder channels. Because of its constricted size, only a limited amount of polymer melt may be dragged
through this zone depending upon the screw rpm. Since the metering zone does not allow the entire material coming to the
compression zone to pass through, the excess polymer is pushed back resulting in continuous mixing. At the end of the metering zone
is the head of the extruder screw, which may have spikes (optional feature) for further mixing/homogenization.
Mass flow rate = volume between teeth x no. of teeth in a gear x 2x rpm x density of melt
The volume of gear pump and its efficiency of pumping may be estimated as per the description given in the literature.
5.What is a spin pack?
Spin pack is the heart of the spinning system ( Figure 2.4 ). It has a reservoir of polymeric fluid-that dampens the pulsating effect of
the gear metering pump, a filter pack- that removes the solid particles from the melt. These may be polymer gels, agglomerated
additives, contamination, etc. Normally a filter is a set of filters containing 3-5 individual filter meshes, where the first filter is a coarser
filter followed by the finer ones. The lowest filter is the finest of all which makes sure that no particle other than those desired (such as
well dispersed micron sized particles of an additive such as TiO , a delustering agent often used in fibres) is pushed through the
2
spinneret hole. Improper filtration will clog the spinneret hole leading to a lower throughput and a lower denier of that filament, and
eventually, result in a break of the spinning filament.
along with the delicate freshly spun filaments. The filaments are given a spin finish at the end of the spinning line (just after the glass
transition is reached) by one of the many techniques- kiss-roll or spray. The finish is normally sprayed onto the filaments in high speed
spinning machines.
The roles of the spin finish are to provide (i) lubrication- to reduce friction between the yarn and the metallic/ceramic parts of the
spinning line, (ii) antistatic property- to allow dissipation of static charge generated due to contact of yarn with the machine parts and
(iii) cohesion- to keep the filaments of a yarn together, so that unwinding becomes easier from the spun cake. Lubrication is provided
by aliphatic/alkyl molecules, which have very low van der waals attraction among them. Antistatic properties/cohesion is provided by
polar molecules, which have strong hydrogen or ionic bonding and provide path for charge dissipation. Since a spin finish needs both
types of molecules, it is generally made by emulsifying alkyl chain molecules with the help of surfactants in aqueous medium. A
balance of the two ingredients is important to achieve an optimum of all properties needed in a spin finish.
Readers may refer to literature for information on spin finish functions and its formulation.
9.What is a take-up winder?
The next important device is the take-up winder. Usually, the yarn is not wound directly on the winder but is passed through a take-up
godet, or a set of godet rollers ( Figure 2.1 ). This breaks the vertical path of the spinning and allows the winder to be adjusted
comfortably in the available space. Also, in an integrated system, the spun filaments may be subsequently drawn between the two
godets before winding (also known as in-line spin-draw frames). The spinning speed is decided by the speed of the first rotating
surface the filament comes in contact after the spinning chamber. This can be the first take-up godet or the take-up winder if the spun
filaments are being directly wound onto the winder without breaking their vertical path.
The winders may be friction driven ( Figure 2.6(a) ), where the bobbin is driven by a friction roller so that the surface speed of the
winder remains constant through out the formation of the yarn package. However, now a days, godets and friction rollers are not being
used in high speed spinning plants. This is because the yarn when comes in contact with such surfaces can be abraded and may
result in poor quality or poor wind-up. Therefore, new winders are used that have bobbins which are directly driven by a motor. In order
to compensate for the increasing speed as the diameter of the bobbin package changes, an auto feed back mechanism is installed
where the speed of the winder is regulated to maintain constant tension in the spinning line (Figure 2.6(b) ).
Figure 2.6: Schematic representation of (a) friction winder, (b) straight
winder
where k is a constant; n = 1 when the weight average molecular weight (M ) of the polymer is below a critical molar mass M ; and
w c
n = 3.4 for M above the M as shown in Figure 2.7. In case of polymer solutions, this critical point is defined by the critical molar
w c
Figure 2.7:
Dependence of shear viscocity on molecular
weight and shear rate of a polymer
Where is the activation energy for flow and R is the gas constant.
There are many other factors besides molecular weight and temperature on which a polymer fluid shear viscosity would depend.
The important factors are shear rate, time, pressure, molecular weight distribution and molecular branching/pendant group size,
etc
The behaviour of a polymer is quite complex and to have a little better understanding, it may be thought of as a bowl of long and
thin worms (a physical model). Each worm may be considered to be 10 m long and only 1-2 millimeter in diameter. It may be
imagined that these worms in this bowl can not move independently, because they are all intensely entangled with each other.
They can only move their body in parts at a time (equivalent to segmental motion in polymers), and make adjustments at each
entanglement (similar to relaxation in polymer chains). If this bowl of worm is put under a net external force in a particular
direction, the entire group of worms will slowly move by wriggling one portion of their body at a time and adjusting (slipping)
through various entanglements. If on the other hand, this bunch is pushed out and then released immediately, they will show
rubber like elasticity and will rebound back to nearly the original space and position occupied earlier to the application of external
force. However, if they are pulled slowly, while given enough time for adjustment, they will move permanently by a small distance
on application of comparatively lower level of external force. Also, if the bunch of worms are continuously pulled at a certain rate,
they will slowly disentangle with the elapse of time, and the resistance offered by them will get lowered with time. Similar to this
model, the viscosity of the polymer fluid is dependent on the rate at which the material is moved (shear rate) and also the time
for which it is moved at a certain rate (time dependence).
The free space among worms would depend upon their internal energy level (which is reflected by the intensity of mobility of
their body parts) and would decide the resistance a group of worms would offer to each other when a force is applied to make
them move. This is similar to the case where a lower resistance is experienced by the polymer chains at a higher temperature.
Similarly, presence of short side chains or pendant groups increases free space between two chains, and therefore, would tend
to reduce the viscosity of the polymer fluid. Such chains with pendant groups are also more stiff relative to the perfectly linear
chains and therefore, their critical chain length (i.e. critical molar mass, M c) at which entanglements take place, is also higher.
Therefore, the polymers with side chains are processable at low temperature. However, if the side chains or branches are long
or dense, they may get into entanglements of their own and raise the viscosity.
On the other hand, increasing pressure on a fluid would have an opposite effect on these worms (molecules) and will bring them
closer to each other, reducing their free space, and would result in increasing the resistance to flow.
The readers may find this model helpful in understanding the behavior of polymeric fluid under various situation of fibre spinning.
The above model also explains the inherent elasticity (i.e. tendency to bounce back) that a polymer fluid exhibits along with the
viscosity (i.e. tendency to assume new position). Elasticity is explained in more detail in the following section.
Viscous fluid flow types
(a) Newtonian behaviour
Polymeric fluids may be approximated to Newtonian fluids at very low shear rates. A Newtonian fluid is one where
viscosity is constant at a given temperature and pressure and the stress in direction perpendicular to the flow is
proportional to the velocity gradient or shear rate
For such a fluid, the velocity profile and flow rate through a cylinder (ignoring its end effects) is given by
Where is the velocity of fluid in direction z (i.e. cylindrical axis) at a radius r and Q is the volumetric flow rate of the fluid
flowing through a cylindrical pipe of radius R and length L under a pressure difference of P applied across the cylinder length
L.
This is known as Hagen-Poiseuilles law. The above relations suggest that the fluid moves in a parabolic velocity profile as
shown in Figure 2.8. The velocity of the fluid increases with increasing pressure difference applied between the two flow points
and decreases with increasing viscosity of the fluid. However, the flow rate of the fluid is strongly dependent on the radius of the
cylinder. This implies that to move a viscous polymer through a fine hole, a very high pressure would be required. Therefore, in
melt spinning, the entire spinning line including spin pack is built to withstand high pressure.
Figure 2.8: Representation of shear flow in a
cylinderical pipe
(b) Non-Newtonian behaviour
Polymeric fluid is usually not a Newtonian fluid. This means that the viscosity of the polymeric fluid is a function of shear rate.
Though polymeric fluids may be approximated to a Newtonian fluid at very small shear rates, their behavior deviates
considerably from a Newtonian Fluid at higher shear rates. These can be termed as non Newtonian fluids. Polymers are not just
simple non-Newtonian fluids but show complex behavior, which means that the viscosity of the fluid changes not only with the
shear rate but also with time. This behavior is a result of viscoelastic nature of the polymer fluid.
Flow rate of a non-Newtonian fluid may also be expressed by Hagen-Poiseuilles equation, where instead of Newtonian
viscosity, apparent viscosity of fluid at a given shear rate and history (i.e. time) is used.
The above value (P ) represents the pressure needed to overcome the viscous forces of the fluid for this flow rate.
v
Pressure P required to overcome the viscous nature of a polymeric fluid depends upon both the nature and the shear rate of the
v
polymer fluid. Non-Newtonian fluids can be shear thinning or shear thickening. Mostly polymeric fluids are shear-thinning, i.e.
their viscosity decreases with increasing shear rate. This is because the long polymer chains tend to come out of the
entanglements when sheared and tend to exert lower resistance as the shear rate increases. The dependence of viscosity on
polymer molecular weight also changes considerably for a non-Newtonian Fluid at higher shear rates as shown in Figure 2.7.
The shear thinning behavior of the fluid is also dependent on polydispersity index, PDI (molecular weight distribution) of the
polymer. It has been observed that the extent of shear thinning increases with increasing PDI.
(c) Elastic behaviour
Polymeric fluids are not purely viscous, in fact they are visco-elastic fluids. In such fluids, pressure P calculated from the above
v
equation is only part of the total pressure (P ) required to move the fluid at the given flow rate.
T
The energy spent due to residual of applied pressure (P P ) gets stored as elastic energy and is released when the external
T v
forces are removed from the fluid. This implies a visco-elastic fluid behaves both as a viscous fluid and an elastic material. The
elasticity develops from the fact that the polymer chains are entangled with each other (as in the bowl of worms) and are not
totally free to move past each other when a pressure or force is applied. This means that as the polymer is pushed through a
cylinder or any other geometry, part of the energy (force x distance) is utilized in moving the fluid permanently i.e. by overcoming
the viscous nature and the other part is spent in compressing the fluid network, i.e. this energy gets stored as the elastic energy
in the polymer chain network. As and when the fluid is freed from the applied force, the compressed elastic network tends to
bounce back to its original position. However, the polymeric fluid is not very highly elastic and keeps losing its stored elastic
energy with time due to relaxation of entanglements. Had the polymer been completely elastic (such as a network of connected
springs), it would have completely rebound to its original position and no permanent movement would have taken place. But this
is not the case in polymer fluid because the chains are not permanently locked in entanglements with each other and they do
move slowly (slip, adjust, or even come out of it) relatively to each other and acquire a new position with lapse of time. Figure
2.9 depicts the role of visco-elastic nature of a fluid polymer during its movement.
Figure 2.9 : Schematic representation of entanglements of
polymer chains under various stress conditons
The elasticity of the polymer network is a function of relaxation behavior of the polymer. This is characterized by the relaxation
time of the polymer. Relaxation time is defined as the time taken by the polymer chain to relax to a new position when put under
stress (force/area). The smaller is this relaxation time, the lower is the elastic character of the polymer because the polymer
network has the ability to adjust or move easily and permanently to a new position. Since relaxation of a polymer melt is faster at
a higher temperature and with lower molecular weight, the elasticity of the polymer network is lower for shorter polymer chain
polymers or for polymer at higher temperature.
The elastic behavior of the polymeric fluid is also a function of shear rate. If the polymer is sheared at a faster rate, it shows
higher elasticity. This is because chains get lesser time to relax from the original entanglements. Therefore, much higher
pressures, due to increased elasticity (P P ), are required to move such fluid at higher shear rates.
T v
Therefore, in a viscoelastic fluid, at higher shear rates, there are two competing effects- one that tends to lower the resistance to
flow due to shear thinning effect, and the other, that tends to increase the resistance to flow due to increased rate of elastically
stored energy. Various parameters may be used to control or modify the visco-elastic behavior of a polymer system in melt or
solution. This relative degree of viscous and elastic nature of the polymer fluid plays a critical role in fibre formation during
spinning. This is discussed later in this module.
sile stress and is the strain rate or extension rate of the fluid. When , elongational viscosity, is a constant, the fluid is known a
Fluid. Otherwise it is called non-Troutonian fluid.
howing both Newtonian and Troutonian behaviour,
luids are non-Troutonian, which means their elongational viscosity changes with the strain rate when tensile forces are applied. At small stra
ay be approximated to Troutonian behavior. At higher strain rates, if elongation viscosity increases with increasing strain rates, the polymer f
n thickening fluids and if it decreases then it is known as strain thinning fluids.
tional viscosity normally builds up with lapse of time at a particular strain rate. As explained earlier for the elastic behavior, it has to do with
stic energy build up versus dissipation due to chain relaxation. Polyolefins show stronger elastic built-up compared to condensation polyme
polyesters. However, the elasticity of polymers is generally more sensitive to the change in temperature than to changes in strain rates. Fig
12 show the elongational viscosity of low density polyethylene (LDPE) and polyamide-6 in relation to time and strain rates.
.11 Effect of strain rate on change in elongational viscosity Figure 2.12 Effect of strain rate on change in elongational visco
with time for LDPE time for nylon-6
1. Thermodynamics
2. Rheology or fluid dynamics
3. Mechanical force balance or rate of momentum balance
4. Heat balance
Thermodynamics
This factor has been briefly mentioned in the previous section. For any process to occur
spontaneously, it should be thermodynamically supported, otherwise, it will not be stable. In
other words, the overall Gibbs free energy of the system must be lowered, or the change in
Gibbs free energy (G) must be negative.
G =H-TS <0
During spinning, the polymer chains which are randomly placed in the molten fluid are
elongated and oriented in the direction of spinning. This implies that the entropy of the system is
forced to be lowered because the spun fibre is a more ordered structure.
Because of this TS becomes negative and the overall contribution of this term (-TS) is
positive to the Gibbs free energy. At the same time, enthalpy of the system rises because the
surface energy of the system rises, giving another positive change to Gibbs free energy. This
implies if the polymer is simply oriented and left without introducing any other change in its
structure, it will slowly shrink back to the randomly coiled form with lapse of time or when
sufficient energy (above its glass transition) is provided to this system. Such a spun fibre would
not be stable.
Therefore, for the spun fibre to become a stable structure, the polymer system must undergo change in
enthalpy in such a way that the net contribution of all the terms to Gibbs free energy is negative. This will
occur only if the enthalpy of the system lowers. Lowering of enthalpy occurs as the polymer chains come
closer upon orientation. This reduces free space among polymer chains and improves their intermolecular
interactions by a considerable extent. This also results in polymer undergoing phase change at some
regions i.e. crystallization. This improvement in intermolecular interaction, which is indicated by the
formation of a more stable structure, having characteristic feature of strain hardening, results in lowering
of the overall enthalpy of the system, i.e. H< 0 . However, it is important to note that only if the decrease
in H is large enough to compensate the decrease in entropy due to orientation and increase in enthalpy
due to surface tension, that the spun materials would be stable.
For spinning to happen, the spinning system should provide conditions that will induce phase
change as soon as the polymer has undergone desirable deformation. This phenomenon is
facilitated by rapid cooling of the filament under spinning stresses. Temperature of cooling air,
its humidity, and flow rate are some of the spinning parameters that decide the cooling rate and
position at which the filament under goes melt crystallization, and subsequently, solidifies (i.e.
achieves glass transition temperature) in the spinning line.
Melt spinning concepts: Fluid dynamics
As mentioned earlier, spinning of polymer into filaments involves two types of fluid flow- one is shear flow before the extrusion
i.e. flow through a spinneret and the other is elongational flow (extensional flow). These flows have to be in a stable region in
order for the spinning to occur without defects or breaks in the spun filament. In most polymer production operations, the
production rate is often limited by the onset of flow instabilities. Therefore, understanding the causes for fluid instabilities is
important for successfully carrying out spinning of a polymer fluid.
Extrudate Swell
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.
Solutions of polymer show much lower extrudate swell because the polymer chains are placed apart from each other due to the
presence of the solvent around the chains. The elasticity of the polymer solution is very low compared to that of polymer melt.
Therefore, the L/D ratios in spinnerets for solution spinning are often small i.e. ~1. Also the spinneret holes are not separated
from each other by a large distance.
In a polymer solution, the extrudate swell increases with the increase in the polymer concentration besides other factors as
discussed above.
Application of the downward tensile force in the spinning zone also helps in reducing the extrudate swell of an extruded filament.
This is possibly because of the applied spinning forces on the polymer network that facilitates the polymer to relax more in the
spinning direction than in the lateral directions.
(b) What is 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. For a series of linear low density
polyethylene (LLDPE), the critical rate is proportional to the molecular weight raised to the power -5 . For
the same series of polymers of a given molecular weight, the optimum melt fracture performance has been found to be at a
specific polydispersity value. This is shown in Figure 2.13 where the value of apparent shear rate for onset of melt fracture has
been plotted against polydispersity. Initially, as the polydispersity increases, the onset value also increases slowly, at a critical
value, between 8.6 to 9.6, the apparent shear rate for onset increases sharply giving the best performance in extrusion. Below
polydispersity of 9.6, the melt fracture is of shark skin type (low amplitude, high frequency). Above the polydispersity of 9.6, the
onset values start to decrease again, and a wavy type melt fracture (high amplitude and low frequency) is seen to occur. Figure
2.14 shows the typical melt fractures obtained below or above the critical polydispersity values for a series of LLDPEs. It is not
known whether similar phenomena will be observed for other polymers, HDPE or PP. However, it is expected that polydispersity
will have a strong influence on the shear rates for onset of melt fracture.
Solutions, being dilute, normally do not show melt fracture. However, if melt fracture occurs, then an additional factor that
increases onset of melt fracture is the increasing concentration of the polymer solution.
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.
Figure 2.13: Dependence of critical Figure 2.14: Typical fractured
shear rate on polydispersity index extrudate appearances of
(PDI) polymers
Draw resonance
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.
Which types of fluids show draw resonance?
This phenomenon has been observed in both, Newtonian and Power-law fluids (non-Newtonian) and is experimentally found to
be closely related to polymer properties (molecular structure, molecular weight distribution, shear viscosity, relaxation time,
power law index) as well as to the spinning variables such as draw ratio, cooling rate, melt temperature, die geometry etc.
There are many different disturbances to melt spinning process that can trigger the onset of instability. Change in material
properties of fluids like viscosity, elasticity, thermal capacity, and density, etc. represent one group of disturbances while change
in processing conditions of spinning like spin-line velocity and temperature, spinning distance, cooling air velocity and
temperature etc. pose as another group of disturbances. For example, the draw resonance may initiate because of the
occurrence of fluctuation in the polymer throughput or the take-up speed at the winder or take-up roller. The throughput may
change because of the fluctuation in pressure or viscosity (due to change in spinning temperature).
Draw resonance is a hydrodynamic instability not a viscoelastic one, albeit altered by fluid viscoelasticity, thus, even Newtonian
fluids can exhibit it. It has been reported both theoretically and experimentally, that a Newtonian liquid sustains in-phase
oscillations in force and area at draw ratios ~20. Hence, critical draw ratio for Newtonian fluids is taken as ~20. This is true for an
isothermal spinning system.
The types of draw mode in a spinning zone
The parameter where A is the area of fibre, v the velocity at distance z from the spinneret, can be defined as the
local draw mode and indicates three characteristic draw modes:
Condition (i) means a larger cross-section of filament will be stretched to a larger extent than that having smaller cross-section.
This draw mode can be stated as uniformizing draw mode because it tends to remove thicker places in the spun filament.
Condition (ii) is satisfied when all sections of the filament are stretched to the same extent described as a uniform draw mode.
In condition (iii), smaller cross-sectional areas of the filament get stretched more and the condition is defined by non-
uniformizing draw mode ( Figure 2.15).
Figure 2.15: Representation of various
drawing modes of spinning fibre
Isothermal melt spinning under uniform stress for power-law fluids is an instant of uniform draw mode. Also, in such a case, the
velocity gradient is constant. Solving the governing equations of melt spinning it has been found that whenever the take-up
velocity and extrusion rate are kept constant, no cross-section area variation in the taken-up filament will be observed. Thus, it
indicates that non-uniformizing draw mode is the necessary condition of draw resonance.
Draw resonance in Real-time melt spinning
An alternate expression of draw mode can be obtained by differentiating w.r.t. distance z,
Using the above equation, we can calculate qualitatively, the draw mode from the velocity profiles of spin-line. In this case, the
velocity profile can be separated into two regions ( Figure 2.16), unstable region (iv) wherein the contributions of cooling,
molecular orientation etc. on viscosity are small and so the thinner sections get stretched to a larger extent. This may happen
because usually polymers show a strain thinning behavior when in completely fluid form. Since thinner sections have higher
stresses (spinning forces per unit cross-sectional area of the filament), they extend at a higher strain rate resulting in lowering of
viscosity, which further enhances thinning of already thin sections. Whereas, in stable region (vi), the polymer turns strain
thickening due to cooling and molecular rearrangement (i.e. orientation and stress induced crystallization). Since strain
thickening polymer shows higher localized viscosity at thinner sections, thicker sections tend to extend more, resulting in
uniformizing draw. Hence, draw resonance is suppressed in this stable region, which indicates why draw resonance is rarely
observed in real melt spinning.
thread-line residence time (T , time taken by the fluid to travel from spinneret to the take-up). This is because the throughput
L
passing through the system in one period of draw resonance must be constant.
The following solutions are applicable in the region from the die swell to the end of the spinning line.
(1) Newtonian fluids: In this case, throughput wave velocity is a function of the draw ratio only. Neglecting the effect of
secondary forces such as inertia, gravity, and surface forces on the thread-line, and assuming uniform velocity distribution
across the thread-line cross-section and origin starting from the extrudate-swell region, the traveling time of a throughput wave
is:
t = (L ln(r)) / v (r-1) .......... (1)
L o
Hence, in accordance with the earlier explanation, the onset of draw resonance is when,
2t = T ............(3)
L L
The above equation is satisfied for . r = 19.744 (or ~20). This is shown in Figure 2.17. Therefore, the value of critical draw
ratio for onset of draw resonance in isothermal spinning of Newtonian fluids is ~20.
From equations (1), (3) and (4), we conclude that the critical draw ratio is less than 19.744 if the power law exponent n < 1 and is
greater than 19.744 if n > 1 (Figure 2.18). This means that a strain thinning fluid tends to increase the draw resonance tendency
and the critical draw ratio at which the fibre is not spinnable decreases, while for strain thickening fluids, the limiting draw ratio
increases substantially.
Figure 2.18: Dependence of critical draw down ratio on exponent of power
law fluids
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 T and then set into a new form. This type of set is maintained with normal
g
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 T . g
(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 T becomes lower as their moisture content increases. Since
g
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).
Similar to PET, even in nylon 6, drawability of the as-spun material reduces with the increasing spinning speed, owing to
increased deformation of polymer network. Figure 4.4 shows a series of true stressstrain curves for undrawn nylon 6 yarns
obtained over a wide range of wind-up speeds (5006500 m/min) that have been shifted horizontally to coincide with the 500
m/min LOY curve. For yarns spun at wind-up speeds below 4000 m/min, a good fit with the first curve is obtained indicating the
presence of substantial NDR (characterized by a flatter region). For yarns spun at wind-up speeds above 4000 m/min, on the
other hand, the shifted true stressstrain curves coincide with the first curve only in the final strain-hardening regime. This
indicates that network topology changes with increasing wind-up speed. A transition in structure-formation mechanism occurs at
wind-up speeds of about 3000 m/min, associated with the onset of spin line crystallization.
relax and recover some part of the machine draw ratio applied to it. Eventually, the fibre may attain a draw ratio called 'actual
draw ratio', given by final length to the initial length, which is equal to or less than the machine draw ratio depending upon the
amount of relaxation the fibre undergoes. The speed at which the fibre travels between the two rollers determines the rate of
drawing. An estimate of this draw rate can be worked out as follows:
The average speed between the rollers is (V + V )/2; if the distance between the draw rollers is L, then the time spent by the
1 2
Figure 4.6: Spin-draw process for a high performance nylon-6 tire cord
manufacturing
By analogy to amorphous polymers, the term cold drawing has been expanded to semicrystalline polymers. This was promoted
by the circumstance that exterior attributes of cold drawing, i.e. necking and the specific shape of stress-strain curves, are
observed for semicrystalline polymers also. However, many semicrystalline polymers can deform with necking at temperatures
that are considerably higher than their glass transition.
Therefore, for semicrystalline polymers, the cold drawing is defined as any large strain of a sample (without dependence on neck
formation) accompanied by large amount of plastic deformation, but with some portion of elastic deformation. During cold
drawing, plastic deformation results in a substantial transformation of structure, associated with processes of crystallization or
melting/recrystallization.
If a semicrystalline fibre draws without undergoing such transformations, it would recover back to original dimensions after the
drawing stresses are removed. This is called rubber flow deformation drawing.
In hot drawing (flow deformation drawing), only plastic deformation or flow processes are observed.
The mechanism of neck formation in cold drawing is believed to consist of three main stages (Figure 4.7) : (a) Initially, the fibres
resist the deformation similar to an elastic material. In this region fibre tends to maintain its original shape and undergoes
uniform stretching. (b) Thereafter, a critical point is reached, where some portion of the fibre, due a mechanical irregularity, is
unable to bear the localized stress and fails (i.e. deforms). This initiates catastrophic break down of the remaining structure as
well and the fibre undergoes rapid deformation by forming a neck. (c) Lastly, this deformation continues till it removes the natural
draw of the material. The level of stresses is high in the neck, and therefore, the polymer chains are able to orient and undergo
stress-induced crystallization during neck drawing. This stabilizes the structure of the fibre by forming a more stable elastic
network. (d) As soon as this network is formed, the fibre is able to resist the applied drawing stresses and further deformation.
This forms a drawn and stabilized fibre. Most of the drawing takes place through this mechanism.
Figure 4.7: Various stages in cold drawing leading to neck formation.
The temperature-interval of cold drawing is defined by the brittleness temperature, on the one hand, and the temperature of the
supermolecular mobility from the other. The temperature of supermolecular mobility, T , approximately equals 0.80.9 of the
h
melting point of a polymer on a Kelvin scale. Above T , but lower than the melting point, hot drawing is realized. In this
h
temperature interval, mobility of large supermolecular elements (such as fibrils and crystallites) are observed without their
fracture during sample deformation.
be maximized for a given as-spun fibre by subjecting the fibre to the optimum drawing parameters.
At this point, the readers must also recall, that the state of polymer chains (i.e. entanglement density has profound effect on the
drawability of the fibre. Both very high and very low entanglement density may lead to a poorer value even at optimized
max
drawing parameters.
Advantages of multidstage drawing
As mentioned earlier, cold drawing is more effective in producing a well connected oriented structure than drawing during melt
spinning. Therefore, for producing high performance fibres, the fibres are normally spun at low spinning speeds to produce LOY.
This allows the as-spun fibres to be drawn to very high draw ratio of ~5-6 for achieving high orientation. Such drawings are
effectively carried out by using multi stage drawing rather than single stage drawing. During drawing process, the stresses are
not distributed equally on all chains because of randomly existing tie points (crystallites or entanglements) and certain high
stress points are created. If such a system is stretched further to a large draw ratio, many of these high stress points may
produce defects such as chain breakage or crack propagation. It is important that the fibre is allowed to relax and adjust after
partial drawing so that stresses at high stress points are dissipated. Multi stage drawing allows fibres to be drawn or stretched in
steps with relaxation built in to large draw ratios without fear of producing defects. The second advantage of multistage drawing
is that fibre may be subjected to correct temperature of drawing as the draw ratios are increased. On drawing,fibre starts to get
oriented and undergoes stress induced crystallization. This increases the glass transition temperature (T ) of the fibre and
g
drawing at low temperature becomes difficult to achieve high draw ratios. In multi stage drawing enough mobility may be
provided to fibre by increasing the temperature as the fibre structure changes with each step of drawing. This allows efficient and
defect free drawing unlike in single stage where only one temperature can be kept.
Copyright IIT Delhi 2009-2011. All rights reserved.
Structure development during drawing
Drawing is associated with significant changes in the structure of the fibre. Due to the high stresses developed during drawing,
the orientation of fibres increases, crystallinity usually changes, and type of crystals may undergo transformation. The
morphology of the structure may also change from micellar to fibrillar, with concurrent change in connectivity between
amorphous and crystalline phases. Overall change is to lower Gibbs free energy (G) by lowering enthalpy (H) of the system.
a. Orientation development
The network draw ratio reflects the state of deformation of the molecular network present in the undrawn and drawn fibres. It is
of interest to look at the development of molecular orientation with network draw ratio, since this provides insight into the
mechanisms of deformation throughout fibre processing. There are two theoretical schemes for prediction of orientation from
network deformation: the affine and pseudo-affine deformation mechanisms. In the affine scheme, network junctions are thought
to be connected by flexible chains. Upon stretching, the network points are displaced in direct proportion to the macroscopic
deformation. As a result, the rotatable random links comprising the network chains gradually adopt a more and more oriented
configuration. This is a rubber-like deformation, where the orientation parameter <P > can be described as a function of the
2
-----[4]
Where n is the sample birefringence, n is the intrinsic birefringence and N is the number of random links between network
max
points.
In pseudo-affine deformation, the structural elements undergoing deformation are assumed to be rigid entities having no
extensibility themselves. These simply rotate in proportion to the macroscopic deformation of the sample. Here orientation
parameter is given by equation [5]:
-----[5]
Figure 4.9 : Crystalline and amorphous orientation factors f and f of c a
the highest draw ratios. The crystalline phase responds to draw ratio in a pseudo-affine fashion whereas the amorphous phase
follows a rubber-like, affine deformation. Crystallites act as rigid entities in the fibre structure whereas the amorphous phase
consists of flexible chains, acting as a rubber network. On drawing of a semicrystalline sample, the amorphous orientation
remains comparatively low even at the maximum draw ratios because drawing of amorphous phase is hampered by the
crystalline phase.
The early work of Ward and co-workers has shown that orientation development in PET fibres spun at low spinning speeds
follows the affine deformation theory of rubber elasticity. Whereas in nylon-6, pseudo-affine mechanism is dominant. The
difference between nylon-6 and PET in this respect can be attributed to differences in crystallization behaviour of the two
polymers. Nylon-6 has a lower T than PET and the T of nylon-6 shows a pronounced dependence on moisture content. As a
g g
result, nylon-6 fibres tend to rapidly crystallize after winding and conditioning, even if crystallization does not occur in the
spinning thread itself. This means that undrawn nylon-6 yarns are always partially crystalline, irrespective of wind-up speed. In
contrast, undrawn PET yarns produced at low speed are nearly fully amorphous and develop moderate levels of crystallinity only
at wind-up speeds sufficiently high to induce spin line crystallization.
b. Change in crystallinity during drawing:
Whereas the degree of orientation always increases in the course of drawing, the crystallinity can change in both directions.
Three types of behavior can be distinguished
1. Deformation is accompanied by additional crystallization and an increase of crystallization.
2. Deformation does not affect phase structure: an undrawn amorphous sample remains amorphous after drawing; a crystalline
sample does not change its degree of crystallinity.
3. Deformation is accompanied by partial destruction of the original structure and reduction of crystallinity.
Orientation of the polymer chains may be accompanied by change in crystalline region. However, it is not necessary that the
crystallinity will always increase with drawing. In a semicrystalline thermoplastic polymer with low crystallinity, the orientation is
normally accompanied with increase in crystallinity. Example is POY PET drawn at neck drawing conditions at high draw ratio.
However, if the polymer is already at an equilibrium state as far as crystallinity is concerned such as wet spun fibres, where
crystallinity has developed to the full extent in the coagulation bath itself due to high mobility of the chains, no further increase in
crystallinity is observed on drawing. Alternately, if the material is drawn at a very slow rate (flow deformation) at a low
temperature so that thermal crystallization does not take place, then also, change in crystallinity is negligible. Example is drawing
of amorphous PET at a slow rate in a cold bath.
In some other instances, crystallinity may decrease as the fibre is drawn. This may occur if the starting fibre has high crystallinity
and due to applied stresses of drawing, small imperfect crystallites may get deformed or broken. For example, a fully crystallized
PET sample drawn forcibly at a high temperature may result in lowering of crystallinity with drawing.
(c) Change in crystal type during drawing
In many fibres, initial crystal type may get transformed as the fibre is subjected to drawing stress. In this, crystal type of high
energy may get transformed to more stable crystals (crystal type of low energy). For example smectic phase of PP transforms to
(alpha) crystalline phase on drawing. Similarly, (gamma) crystals in nylon-6 are transformed to on drawing. The alpha type
structure in nylon-6 possesses hydrogen bonding between antiparallel chains while gamma type structure possesses hydrogen
bonding between parallel chains. The gamma type structures generally have a shortened crystallographic repeat distance in the
direction of chain axis.
In materials, where there is only one type of crystal, imperfect crystallites formed during spinning stress may get transformed into
more stable and perfect crystals during drawing.
(d) Changes in long-range morphology of the fibres
The morphology of the structure may also change from micellar to fibrillar, with concurrent change in connectivity between
amorphous and crystalline phases. Overall change is to lower Gibbs free energy (G) by lowering enthalpy (H) of the system.
Long range order is important in fibre morphology. This decides the formation of fibrillar structure, which is more load bearing.
Also, it decides the manner in which crystalline and amorphous regions are connected to each other for load transfer. It is
observed that length of long range order reduces with shear of drawing stresses. However, if the drawing temperature is
sufficient, the long range order may improve as the fibre is drawn.
Instabilities in drawing
Instability in drawing may arise due to three reasons; the starting material, the drawing parameters, and the drawing machine.
(a) Starting material: If the starting material is non uniform along its length, for example, having thick and thin places or having
different levels of crystallinity, etc., the fibre may show unstable drawing. The non uniformity in the samples lead to nonuniformity
in drawn fibres with initial defects amplified to a great extent.
(b) Drawing Parameters: If the drawing tension is too high, because of drawing parameters, the drawing may not stable. This is
because any small difference in material morphology would result in magnified changes in the tension of the drawing filaments.
Also, very high or very low DR may induce instabilities. Too low draw ratio may give a dancing neck and portions of drawn and
undrawn material along the length of the drawn fibre. At high draw ratio, the fibre may tend to break or develop defects.
(c) Machine: The eccentricity (non circular form) in machine parts such as feed or drawing rollers, improper control of speed or
drawing temperature may all lead to fluctuations in drawing and give periodic instability or non uniformity in drawn material.