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7.

SMART/FUNCTIONAL SPECIALITY FIBRES


7.3 Bicomponent and Micro Fibres (2 Lectures)
Bicomponent Fibres
Bicomponent fibres are filaments made up of two different polymers that are extruded from the same spinneret
with both polymers contained within the same filament but separated by a fine plane. The two polymers differ in
chemical nature or physical properties such as molecular weight.

Why Bicomponent Fibres?


The conventional fibres may not have all the desirable properties. By the use of bicomponent fibres, the
functional properties of both the components can be exploited in one filament. Further, the fibres can be
produced in any cross-sectional shape or geometry.The properties of these bicomponent fibres are governed by
:
Nature /properties of two materials
Their arrangement in the fibre
Relative proportion of the two
Thickness of the fibre

Types of Bicomponent Fibres:


These fibres can be produced in many geometrical arrangements. On the basis of cross section, these can be
classified as

Core-sheath

Side by side

Segmented pie or citrus fibres

Islands in the sea

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

Spinning of Bicomponent Fibres


For proper spinning of two components it is required that:
Viscosities of the two polymer fluids are comparable. The viscosity should be high enough to prevent
turbulence after the spinneret
Drawability of the two polymers should also be comparable, otherwise splitting may occur
Compatibility of both components with the spinning method that is melt spinning or solution spinning is
also important

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.

Figure 1. Photograph of a Bicomponent Spinning Machine


Figure 2. Sketch showing parts of Bicomponent Spinning Machine
Core-Sheath Bicomponent Fibres

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

Side by Side Bicomponent Fibres


These fibres contain two components lying side-by-side. Both components are divided along the length into two
or more distinct regions. These are generally used to make self-crimping fibres due to different shrinkage
characteristics of the two components. In some applications, different melting temperatures of the fibres are
taken advantage of when fibres are used as bonding fibres in thermally non woven waves.
Generally, the two components must show good adhesion. however, side by side fibres can also be used for
producing the so called splitable fibres which split in a certain processing stage yielding fine filament of a sharp
edge cross section.
Figure 5. Schematic showing melt spinning of side by side bicomponent fibres
Multi layer fine or microfibers
After the commercialization of self-crimping bicomponent fibres in 1960s, attempts were made to multiply the
conjugating structure to produce much complicated bicomponent fibres, also sometimes referred to as
multilayer fibres. After development of multilayer fibres around 1965, the fibres were split (as shown inFigure
6) to produce super fine fibres /microfibres

Figure 6. Evolution of Microfibres


Besides direct spinning most other techniques for the production of microfibres involve the spinning of a
multicomponent filament from which smaller sub units are isolated by splitting. Some examples of microfibres
produced by separation /splitting are summarized in Figure 7.
Figure 7. Microfibre produced by separation/splitting
Segmented Pie

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 9. Schematic showing melt spinning of segmented pie structured fibres


PET and Nylon bicomponent fibre is split by soaking in a hot caustic solution of 5-10% NaOH. PET and Nylon are
separated due to swelling.
Figure 10. Schematic showing melt spinning of segmented pie fibres
Sanding and brushing can also be used for splitting fibres. But it works only with fibres that are easily splitable
such as hollow fibre.

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.

Copyright IIT Delhi 2009-2011. All rights reserved.


Synthesis of Modified Polyamides (nylon 6)
Nylon 6 may be modified during the polymerization with comonomers or stabilizers to introduce new functional groups or chain
end groups and thus change the reactivity and chemical properties such as dyeability. Some of the modifications often carried
out for various commercial applications are summarized in Table 1.2 below. In addition, the polyamide fibres can also be
subjected to variety of treatments including chemical, grafting, radiation and plasma, which alter the surface characteristics of
these polymers.
Various Nylon 6 nanocomposite polymers have been synthesized by in-situ polymerization -caprolactam in the presence of
nanomaterials. Nylon 6/nano-TiO and nylon 6/nano-Al O composites have excellent photooxidative degradation resistance. In
2 2 3

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

Table 1.2 : Different modification of nylon-6


Modification Approach By using
Monacid or diacid
By reducing -NH groups
2
Light dyeable nylon 6 stabilizers for blocking -
concentration to 10-15 eq./ton
NH2 groups
By increasing -NH groups 2 diamines to obtain required
Deep dyeable nylon 6
concentration to 25-35 eq./ton quantity of diamines.
Disodium 3,5-
Cationic dyeable By incorporation of sulphonic acid
disulphobenzoic acid as
nylon 6 groups
stabilizer
Antistatic and PEG as a block in the
By increasing hydrophilic groups
hydrophilic nylon 6 copolymer
By incorporating phosphorus/halogen
Flame retardant nylon Alkyl phosphonic acid and
based additives or monomers or nano
6 antimony
clay
Nylon with modified Reinforcement with aromatic Block copolymerizing with
mechanical properties polyamides rigid aromatic polyamide
Modified polyesters
In spite of outstanding properties, such as chemical resistance, easy care properties, resistance to moth, mildew and
microorganisms, the PET fibres have some shortcomings, for example:
Hydrophobic nature
Ease of soiling
Static charge build up
Pilling tendency
Lack of dye receptor sites

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.

Figure 2.2 Schematic diagram of extruder


The design of extruder and its screw may vary considerably depending upon the material being processed and the principal functions
required for processing that material. The readers may refer to other literature for details about the various extruder design and their
functions.
The design of the screw, which includes the length to diameter ratio (aspect ratio of 1:25 or 1:40), angle of the flanges, etc. is kept in
accordance to the specific heat capacity and rheological behaviour of the polymer it is meant to process. Higher the amount of heat
required to be transferred to the polymer, longer is the residence time. For example for PP, since the heat capacity of the polymer is
large and the molecular weight is often high, it needs longer residence time in an extruder to attain lower melt viscosity. A considerable
amount of heat has to be transferred to the polymer to melt it and bring it to the temperature of spinning. Similarly, if a polymer is to be
blended with an additive, the extruder design should allow effective mixing and homogenization, which is again the function of the
residence time and the shear rate.
The design of the screw also has significant effect on the heat generated during shear melting of the polymer, and the energy needed
for melting the polymer chips is provided by both the heaters and the mechanical action of the screw.
2. What is a manifold?
Polymer flows from the extruder to the metering pump and spin packs through a manifold, which is a simple network of cylindrical
pipes as shown in Figure 2.1 . Each pipe is connected to one metering pump. The manifold is designed in such a way, that polymer
takes the same amount of time from the extruder outlet to any of the metering pump whether it is located near or far away from the
extruder. This allows the polymers to have same thermal history, hence the same rheological properties, at all positions of the
spinning. The same residence time is achieved by keeping the length and bends of each pipe same. Also, the pressure drop across
each pipe is kept same so that the polymer gets divided equally. When the distribution lines are long, at times, static mixers are also
installed inside distribution pipes. These allow shear mixing of polymer melt within a pipe to keep it homogenized.
3.What is a static mixer?
A static mixer is a network of channels interconnected with each other like a honey comb web, which takes the polymeric fluid from the
periphery to the centre and that from the centre to the periphery. Also, in this process it induces shear mixing among the various fluid
elements.
Such mixing becomes necessary because in a pipe flow, fluid travels in a parabolic velocity profile, which means the fluid velocity is
maximum at the center and is much lower near the pipe walls. This nonuniform flow profile across the cross-section of the pipe
develops due to the stresses exerted on the fluid by the stationary walls. The shear fluid flow has been explained later in this module.
4.What is a metering pump?
Metering pump has a very important function in spinning as it regulates the through put of the polymer from the spinneret. Throughput
rate and the winding speed (i.e. take-up speed) together decide the denier of the spun filament. A metering pump must deliver
constant throughput irrespective of the back pressure felt by it from the choking filters in a spin pack. Therefore, only the positive
displacement pumps are used for metering polymer melt in spinning.
Typical design of a gear type metering pump is shown in Figure 2.3. The pump has two gears whose teeth are intermeshed with each
other at the center. The gear pair sits in a cavity made into a metal plate and with tip of the teeth in very close clearance from the wall
of the cavity. The polymer enters from the one side of the intermeshed zone and fills the empty spaces between the two teeth of each
gear as they emerge out from the intermesh. This fluid is then taken around the gears by their teeth as shown in the figure. When the
polymer reaches the other side of the intermesh, it is forced out of the spaces between the teeth as the teeth enter the intermesh zone.
The emptied out or pushed out fluid then exits from the other side of the intermesh to the spin pack. The quantity of the fluid passing
through the metering pump is given by the number of teeth getting filled and emptied in a unit time.

Figure 2.3 Schematic diagram of metering pump

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.

Figure 2.4 Schematic diagram of spin pack assembly


It is often believed that if a particle in polymer melt is bigger than 1/10 th of the diameter of the final filament, it will result in a
catastrophic break in the filament during spinning or post spinning operations. Not only should the particles of the additives be smaller
in size, they should not agglomerate to form bigger particles. Addition of additives in polymer melt is a challenging proposition and all
care must be taken to properly disperse the additive particles.
If the polymer is being recycled, often a large amount of dust particles and gel particles are present in the melt. In such spinning lines,
polymer is either filtered using a centralized filtration unit (CFU) located just after the extruder or placing additional filtration medium
such as sand inside the spin pack cavity (melt reservoir) before the filter pack.
Once the polymer is filtered, it reaches a distributor. Function of the distributor, as the name suggests is to ensure proper supply of the
polymer melt to all spinneret holes. Also, it makes sure that there is no dead volume and all the polymer coming to the spin pack is
being utilized in spinning.
6.The spinneret- an important component
The last but also the most important of all components in the spin-pack is a spinneret plate. It is simply a thick metal plate with fine
holes drilled through them as shown in Figure 2.4. The hole has larger diameter towards the inside surface with conical entry. This
allows entry of the polymer melt with less pressure drop. The conical entrance facilitates alignment of the molecules to some extent to
enable them to enter without much force. However, the most important dimension in the spinneret is the length and diameter of the
final cylindrical spinneret (hole). Polymer passes through it in a shear flow and comes out on the other end as an extruded strand.
Spinneret plates for monofilaments have single spinneret hole with diameter of about 0.5-1 mm, while those for multifilament have
several holes with diameters in a range of 0.5-0.05 mm. In case of monofilament spinning, spinneret plate with one hole, spins a single
filament which is wound on a bobbin. The deniers used for such filaments are in excess of 20. However, for multi filament yarn, the
spinneret plate has several holes arranged in a particular fashion and all the extruded filaments from this spin-pack are wound
together on one bobbin to make a multi filament yarn. In a multi-hole spinneret plate, holes are placed is staggered configuration so as
to allow enough separation from each other and to allow cooling air to be available to all the filaments in the quenching zone. Also, the
space between the various holes allows filaments to spin independently without sticking to each other during extrudate swell (also
known as die swell) phenomena (explained later).
The main role of a spinneret is to impart cross sectional shape to the extruded filaments. The cross section may vary from circular to
trilobal, to hexalobal or hollow, etc. Usually it is thought that spinneret is able to orient polymer chains to make a fibre. It is not true.
Spinneret is much bigger than the dimensions of a polymer chain, and hence, can not induce orientation in coiled polymers.
7.Design and role of quench chamber
The extruded filament from the spinneret is allowed to pass through an air quench zone (or chamber). This has mild flow of cooling air
at a low temperature (~15- 30 C) with low to moderate relative humidity. The cooling air when comes in contact with the spun
filaments, takes away their heat and facilitates their solidification. This involves cooling of the polymer past melt crystallization
temperature and eventually to its glass transition temperature. As soon as the glass transition temperature is reached, the spinning is
considered to be complete. This is because, below glass transition temperature, polymer is in glassy state and can not extend any
further. The filament speed at which the polymer reaches glass transition temperature is also the spinning speed of the process.
Thereafter, the speed of the filament does not change and the polymer is wound on a bobbin using a take-up winder.
The uniformity of airflow is extremely important in controlling the variation of filament diameter in a spun fibre. It has been estimated
that a sudden but small change of 1% in quench air velocity may bring about a change of about 0.3% in cross sectional area of the
filament.
The quench chambers may be of various configurations- cross flow or radial flow. In cross flow the cooling air flows from one side to
the other side of the spinneret across the cross-section of the spinning path ( Figure 2.5(a) ). This kind of quench chamber is used
when a limited number of filaments are being spun in a filament yarn. This is because the filaments at the far end (in the direction of air
flow) of the spinneret get air which has been heated by the filaments at the near end. This problem becomes acute when a very large
number of spinneret holes are used in a staple fibre spinning line for making a tow. In such cases 10,000 or more holes are normally
present in a single spinneret. For quenching this large number of filaments, radial flow either of outflow ( Figure 2.5(b) ) or in-flow
( Figure 2.5(c) ) type is used. In outflow ( Figure 2.5(b) ), the cooling air enters at the centre of the spinneret and flows out radially
while in the in-flow type, the air enters from the periphery of the spinneret and flows into the centre of the spinning path. This air then
passes to the take up room along with the filament tow. The radial quenching can accommodate a large number of filaments as more
number of spinneret holes can be arranged in concentric circles. Since filaments get more uniform cooling in radial flow than in cross
flow, the structure and properties of the various filaments are closer to each other. Fibers with delicate dimensions are also spun in a
radial type quench chamber.
Figure 2.5 : Schematic representation of various air flows in
quench zone
8.Spin finish applicator:
Normally the spinning room and the take-up room are separated by a floor and the two have different atmospheric pressure from each
other. The spinning room is at a slightly higher pressure (by 10 mm H O) than take-up room. This allows part of the cooling air to flow
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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

Copyright IIT Delhi 2009-2011. All rights reserved.


Melt Rheology: Shear Flow
During melt spinning, polymer flows through various confined geometries as described above. This type of flow is called shear
flow because the flowing fluid experiences shearing stresses imparted by the stationary walls of the confinement. The shear flow
plays an important part in spinning starting from the extruder where it helps in mixing and homogenization of the polymer melt, to
the spinneret hole where it helps in initiating the process of fibre formation. Therefore, its understanding is important for a fibre
manufacturer.
What is viscosity? How does it originate in a polymeric fluid?
It is the resistance encountered by the fluid during a flow. It originates because fluid molecules interact with each other in
different ways- they collide during movement, i.e. physical hindrance, they interact with secondary forces such as hydrogen
bonding, dipole, ionic, or van-der waals forces. The fluid has to overcome these forces in order to move past each other. In
polymers there is an additional component of resistance that occurs due to the long chains. These are entanglements. The long
chains tend to physically wrap around the other long chains. This offers the highest of all resistances to the flow. Therefore, the
longer the chains, the more resistance it encounters during a flow.
The shear viscosity of Newtonian polymer fluid depends upon the molecular weight as per the following empirical relation:

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

concentration for a given polymer.


Also, the shear viscosity changes significantly with change in temperature by Arrhenius type relation given below:

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.

Copyright IIT Delhi 2009-2011. All rights reserved.


Elongational fluid flow
mer comes out from the confined channels into the open atmosphere, i.e. extruded from the spinneret, its flow behavior changes. It is said t
al flow under tensile forces.
ational flow, polymer fluid flows with a uniform velocity profile perpendicular to the direction of fluid flow. However, it may accelerate, or at ot
s as it travels along its path. Most of the spinning is said to occur due to the elongational flow where fluid velocity keeps on increasing down
e, resulting in unfolding of the polymer chains. Since different fluid elements of a polymer travel at different linear speeds down the spinning
ain tend to uncoil/extend as its ends are caught in different fluid layers traveling at different speeds. This is depicted in Figure 2.10 . Hardly
is gained in shear flow due to the rotating action induced by the shear forces on the fluid.

Figure 2.10 : Comparison of (a) shear flow and (b)


elongational flow
al flow is characterized by the following equation:

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

Copyright IIT Delhi 2009-2011. All rights reserved.


Spinnability
Are all polymers spinnable?
There are several requirements for a polymer to be spinnable. Polymer should be linear and of reasonably high molecular weight so
that connectivity from one chain to another chain may be obtained. The intermolecular forces should be strong and allow
reinforcement of developed structure through orientation and crystallization. There are many polymers that are linear and have high
molecular weight, however, not all are spinnable into fine filaments.
What are the necessary requirements for spinnability?
Polymers exist as a folded structure in melt/solution form. During spinning, a polymer melt or solution is stretched manifolds in a
particular direction to produce a very fine, strong anisotropic entity. This unusually high stretchability of the polymer fluid is possible
only if the long polymer chains have the tendency to unfold irreversibly under the application of small spinning force. This is the first
requirement.
As the polymer is elongated, its surface area increases and this transformation is opposed due to a rise in the surface energy of the
system. Additionally, the oriented chains have lower entropy compared to the starting point, where the polymer chains are randomly
oriented. However, for this deformation to occur and be stable thermodynamically, the overall Gibbs free energy of the system must
be lowered. This is accomplished by improved cohesion of the oriented chains that leads to stress induced crystallization. The
ability of the polymer chains to crystallize is a necessary condition for the spinning to take place because only crystallization could
lower the enthalpy, and therefore, the overall free energy of the system in a spinning process. Crystallization stabilizes the unfolded
structure in the new dimension. This is discussed in detail in the next section.
In other words, if a polymer system can not stabilize with formation of structure with stronger cohesive energy, it would not remain
extended and will fold back to a mass of isotropic fluid as soon necessary energy is available. For example, amorphous polymers,
such as, styrene, PMMA, atactic PP, and polymer with bulky pendant groups are unable to form fibre. This is the second
requirement.
Other requirements of spinnability
Another requirement for spinnability is the ability of the polymer fluid to offer higher resistance to deformation as the fluid is
elongated at a faster rate.
This increase in resistance with increasing extension rate helps in stabilizing the elongating structure with thinner cross-section as it
moves down the spinning line. If this does not happen, the thinned cross-section of the spun filament will go into ductile failure
under the constant spinning force. The resistance to deformation is a result of relative rates of polymer deformation and relaxation.
If the relaxation rate is faster, the polymer is able to deform without much resistance, while if is slower, the polymer network shows
more elasticity. The strain hardening is said to occur when the elastic characteristic of the polymer network starts to dominate.
However, the relaxation rate can not be extremely low. If the relaxation rate is extremely low, it will result in accumulation of elastic
energy to a degree that the polymer network hardening becomes excessive. Under this situation, the polymer will be difficult to
stretch at the desirable spinning speeds and application of higher spinning force may result in a cohesive failure of the polymeric
fluid i.e. breakage of the spinning filament. Therefore, for a polymer to be spinnable, it should have appropriate relaxation time so
that it is able to show controlled strain hardening to avoid ductile failure and at the same time avoid cohesive failure.
Melt Spinning Concepts
Melt spinning is a complex process which consists of several phenomena. These may be broadly classified as:

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.

Instabilities during flow through spinneret


Two types of flow instabilities are observed when polymer fluid flows through a cylindrical path and is subsequently extruded
from a spinneret. These are called melt fracture and extrudate swell (also known as die swell). Both instabilities are due to the
visco-elastic properties of the fluid. Extrudate swell (die swell) occurs, when the fluid is pushed through the fine holes of a
spinneret and is extruded on the other end.
The third type of instability occurs during the extensional or elongational flow of the polymer fluid in the spinning zone. This is
called draw resonance.
(a) What is extrudate 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. This has been explained earlier. 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.

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 RESONANCEFIBER INSTABILITY


(c) 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
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.

Figure 2.16: Different zones of velocity and velocity


gradient observed during melt spinning of fibres
How can draw resonance be explained by Wave Theory?
The exact wave form of draw resonance in isothermal spinning of Newtonian fluids can be sought by numerically solving
equations of melt spinning in their original, non-linear form. When the draw ratio exceeds 20, solutions of the equation become a
limit cycle (sustained oscillation having period and amplitude independent of initial conditions) .
In melt spinning, there exists an invisible kinetic wave (throughput wave) derived from the continuity equation, that travels the
thread-line distance maintaining constant amplitude and a unique velocity. The fluctuation in throughput results in either an
instantaneous increase or decrease in the diameter at the exit of the spinneret hole. This variation (say positive wave) when
travels down the line to the winder induces an opposite change in diameter (negative wave) at the start of the spinning line. In
order to continue this phenomena, or in other words for draw resonance to establish, two such throughput waves, positive and
negative deviations from the mean value, need to travel the spinning distance (from the spinneret to the take-up, t ) in a single
L

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

where, L length of spin-line


r draw ratio in spinning zone

v velocity at extrudate-swell region


o

and the thread-line residence time T is defined as:


L

T = (L (r-1) ) / r (v ) ( ln(r)) ...........(2)


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.

Figure 2.17: Plot of residence time (t and T ) vs draw ratio in melt


L L

spinning zone for a Newtonian fluid


(2) Power-Law fluids: Non-Newtonian behavior of fluids has a significant effect on the draw resonance behavior of the spinning
filament. The important point in case of power-law fluids is that even though the throughput wave velocity is a function of draw
ratio, distance from spinneret, power-law exponent and relaxation time, the threadline residence time is the same as in case of
Newtonian fluids. Considering the same assumptions as in case of Newtonian fluids (i.e. neglecting inertia, gravity etc.), the
thread-line residence time is defined as:
T = L (n-1) (1- r -1/n) / v (r (n-1)/n -1) ...............(4)
L o

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

What are the factors that affect draw resonance?


1 . Process variables
The key link which perpetuates the draw resonance instability is the spin-line tension. Disturbances in the melt spinning system
travel the spin-line in the form of waves which cause the existing spin-line tension to change. This changed tension then brings
about a new disturbance wave which travels towards the take-up. When this new wave arrives, it again changes the spin-line
tension but this time with an opposite sign of the previous change, hence, another wave appears and the whole cycle repeats.
So, the basic mechanism of draw resonance depends upon how well the spin-line tension relays the effect of a disturbance to
the cross-sectional area. The effect of any particular process condition on the stability depends on how much the tension
sensitivity is influenced by the process condition.
2 . Spin-line Cooling
The overall effect of the disturbance on spin-line area decreases with increasing cooling i.e. increased cooling stabilizes the
system thereby reducing draw resonance. Thus, it may be inferred that the stabilizing effect of spin-line cooling depends on
tension sensitivity. The reason behind this phenomenon can be stated as that if the spin-line tension is held on its maximum
limit, its sensitivity to disturbance tends to be minimum i.e., tension sensitivity decreases with increasing spin-line tension.
Another theory suggests that the thinner portions are cooled more rapidly than the thicker ones and so attain a larger viscosity,
thus leading to greater stability. However, the above reasoning for increased stability on cooling holds true only for Newtonian
fluids because in case of non-Newtonian fluids, the effect of fluid viscosity on the severity of draw resonance depends on the
power-law index, as explained earlier.
3.Fluid Elasticity
As discussed earlier, stability of the spin-line depends on the Deborah number, particularly the fluid relaxation time, .
Increasing fluid elasticity increases the value of giving rise to a lower critical draw ratio (at which draw resonance occurs)
than a fluid having a smaller . Thus, it can be concluded that increasing fluid elasticity destabilizes the elongational flow.
4.Molecular Weight Distribution / Long Chain Branching
Studies reveal that under identical spinning conditions, polymers with a broad MWD show a lower melt strength and lower critical
stretch ratio as compared to a narrow MWD polymer. It has also been seen that the extensional viscosity for a narrow MWD
increases or stays constant up to a much higher draw ratio, compared to that of a broad MWD. This increase in the critical strain
with the narrow MWD is responsible for the enhancement in spin-line stability in case of narrow MWD polymers. Also, polymers
with broad MWD are associated with increased extrudate swell and ultimately have a detrimental effect on draw resonance.
Polymeric materials having long-chain branching are reported to have much tighter entanglements as compared to their linear
chain counterparts. These tight entanglements resist stretching by higher strain rates. This may stabilize the draw resonance but
at a cost of good spinnability.

Non Isothermal spinning


Melt Spinning is a nonisothermal process. The temperature of the extruded filament falls rapidly down the spinning line. This
increases the apparent viscosity of the polymeric material down the spinning line, and hence, has a stabilizing effect against
draw resonance. Since the resistance to flow increases, the polymer does not thin down readily and does not show draw
resonance at even much higher draw down ratios compared to the isothermal case.
For carrying out spinning without draw resonance, the spinning draw down ratio should be kept within the limits specified as
above, otherwise the spinning filament may undergo tensile failure.

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).

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

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Introduction to drawing
The as-spun fibres have poor elasticity (inability to recover) and they undergo plastic deformation on application of low levels of
stress. This makes them unsuitable for any application including that of apparel. The polymer chains in the as-spun fibres are in
partially folded conformation and can extend easily on application of stress. Figure 4.1 shows a stress-strain plot of an as-spun
fibre. The elastic region is small and is bound by the yield point that occurs at a low stress and extension level. Following the
yield point, the fibre shows deformation without much resistance till all the chains are unfolded and a new improved (more
elastic) network of polymer is formed. In this region, the polymer chains assume new extended conformation and do not recover
back to their original state when stresses are released. This is known as the region of natural draw and the extensibility is called
Natural draw ratio (NDR) of the fibres. This region of easy extensibility must be removed to make the fibres stable and show
the behaviour of increasing resistance with increasing extension.

Figure 4.1: Stress-strain curves for (A) as-spun and (B)


spun-drawn fibre.
Drawing is necessary to remove the region of natural draw of the fibres. When the fibre is drawn beyond the NDR, polymer
chains form an elastic network with extended conformation in the direction of draw (i.e. along the fibre axis). This gives fibres
higher yield point, strength, initial modulus, and recovery compared to its as-spun form. Figure 1 also shows a typical stress-
strain plot of a drawn fibre in comparison to that of an as-spun fibre. Maximum draw ratio (MDR), in contrast, is the maximum
extensibility a fibre may be subjected to, before it breaks
True stress vs true strain
It is important to remember that the stressstrain curves that are usually drawn while explaining the properties of fibres and the
process of drawing are based on load per unit original denier and strain is calculated based on original length of the specimen.
However, at any point during tensile drawing, the true stress is different because the diameter or the denier of the material is
continuously reducing. Similarly, the true strain must be calculated based on the actual length of the fibre at that moment.
Therefore, as shown in equation [1], true stress is given by
= 0 x DR ----- [1]
Whereas the true strain () is given by the integral of dl/l in the limits of original length to final length, as shown in equation [2]
= ln[L/Lo] ----[2]
If a stress-strain curve is converted to true stress-true strain curve then their behaviour changes as shown for selected standard
curves in Figure 4.2.
Figure 4.2: The stress strain curve vs. true stress or true strain curve
Effect of spinning speed on max. draw ratio
The natural draw ratio in the as-spun fibre is a function of its spinning speed. Figure 4.3 shows the residual extensibility (which
includes region of natural draw) of the fibres with the spinning speed for PET as-spun fibres. The extensibility is about 400-500%
when the fibres are spun at low spinning speeds of 1000-1500 m/min to form LOY filament (loworiented yarn). The POY
filament (partially oriented yarn), which are spun at around 3000-4500 m/min, have the extensibility of around 70-90%. The
extensibility significantly reduces at higher speeds due to stress induced crystallization. A natural draw of about 10% may still be
observed at very high spinning speeds of 6000 m/min or higher. Therefore, the fibres spun at very high speeds may also have to
be drawn though to a much smaller extent.

Figure 4.3: Residual extension versus spinning


speed in PET as-spun filament .
The spinning of fibres at a high speed results in increasing the deformation of the polymer network, however, the spin-draw
imparted to the spinning fibres at high temperature in the spinning line is not able to create a very elastic network of polymer
chains. Fast relaxation of polymer chains at the spinning temperature results in leaving a small amount of natural draw and poor
mechanical properties even when the spinning is carried out at high speeds. For better properties, it is always desirable to draw
the fibre at a temperature just above its T .
g

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.

Figure 4.4: True stress-strain curve of undrawn nylon-6 at various winding


speeds.

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Drawing Machines
Drawing is carried out by simply stretching the filament yarn between two sets of rollers. A typical drawing machine is shown
in Figure 4.5. The drawing occurs between feed rollers and take-up rollers (Draw rollers) at room temperature or at an elevated
temperature by providing a heater plate. The drawn material is given a small twist and is wound on a bobbin as shown in
Figure. The path of the yarn undergoing drawing is regulated by proving guide pins or alternately placing the feed and take-up
(drawing) rollers perpendicular to each other. An idler roller at an angle is provided with each roller set (i.e. feed or draw) to allow
the yarn to be wound in multiple loops separately on each on these rollers. This gives a better grip to the yarn and the yarn does
not slip easily under drawing tension.
The ratio of the surface speed of the draw (V ) and feed roller (V ) is called the 'machine draw ratio'. The fibre after drawing may
2 1

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

fibre during drawing is t= L / (V +V )/2.


1 2
Figure 4.5: Schematic diagram of a typical drawing frame.
If the DR is (which is also equal to extension in fraction + 1) then the rate of extension is measured as shown in equation [3]
Rate of extension = ( 1)/t -----[3]
It must be noted that here the drawing zone was taken as the entire length (L) between the two rollers. However, the drawing
occurs by forming a neck, which is localized in fibre length of a few centimeters. Therefore, the actual draw rate is much higher
than what can be estimated using the above equation.
The drawing is normally carried out by a cold drawing process (explained later) where the fibre is drawn by forming a neck (also
known as neck drawing). The location and stability of the neck is important in obtaining a uniformly drawn filament yarn. A
snubbing pin may be used to help the formation of the neck or to stabilize it in a narrow zone. The drawing is carried out at just
above the T of the polymer. For apparel grade nylon-6, drawing is carried out at the room temperature, while for PET it is carried
g

out at 80C or above.


Drawing may be carried out in a single step called single stage drawing as in apparel grade yarn or in two or more steps called
two stage drawing or multistage drawing, as in high performance tire yarns. There are certain advantages of drawing the
material in more than one stage and these are described later in this section.
Drawing is normally carried out as a separate process on a separate machine as described above, however, at times, drawing
may be combined with spinning machine to provide in-line drawing as shown in Figure 4.6. In such machines heating to the yarn
is provided by using feed rollers or intermediate rollers as heated godets.

Figure 4.6: Spin-draw process for a high performance nylon-6 tire cord
manufacturing

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Neck drawing
Cold drawing or neck drawing of polymers is a frequently used technique for obtaining polymers in an oriented state. The term
cold drawing was initially applied to amorphous polymers stretched in a temperature range between the brittle point and glass
transition. Cold drawing occurs when a fibre sample is forced to extend at a rate faster than the rate of molecular mobility or
relaxation (i.e. a little below T ). At the T , the rates become comparable and the neck disappears.
g g

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.

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Effect of drawing parameters
Effect of parameters on drawing behaviour
As stated earlier, in drawing, polymer chains are unfolded and oriented by applying an external tensile stress in the direction of
the fibre axis. The various parameters that can influence drawing are:
(a) the morphology of as-spun fibre,

(b) the draw ratio,

(c) the draw rate,

(d) the draw temperature and

(e) the moisture content of the fibre.


Depending upon the above factors, the drawing of a fibre may occur as per one of the curves given in Figure 4.8.

Figure 4.8: Family of stress-strain curves shown by a thermoplastic


material.
At the bottom of the plot are curves (type a) depicting flow deformation (hot) drawing. In this, the fibres extend uniformly through
out the length without the formation of any neck. The diameter of the fibre decreases gradually without any abrupt change and
keeps on becoming thin on application of higher and higher stress till the fibre breaks.
The second type of curve (type b) is called neck drawing. As explained earlier, in neck drawing, the fibres draws uniformly (i.e.
gradual decrease in diameter over the length of the fibre) at the initial stage, thereafter, it is followed by formation of a neck
(characterized by a hump) and a nearly flat deformation zone, and finally a strain hardening region, which symbolizes formation
of a stabilized or locked structure. The rapid deformation and the high levels of stress in the neck, orients the molecular chains
and initiates stress-induced crystallization. This stabilizes the structure of the fibre by forming a more stable elastic network.
Most of the drawing takes place through this mechanism.
As we move away from flow deformation curves (type a) to (type c), the natural draw region becomes better defined. However,
on moving more towards (type c), the material starts to lose its mobility and undergoes ductile or brittle failure (type c curves).
Most of the thermoplastic materials show all the three kinds of drawing behaviour explained above. The type of drawing curve
shown depends on the starting material or the drawing parameters.
(a) Effect of drawing temperature: If the drawing temperature is very low, the fibre breaks before it can draw due to limited
mobility, i.e. (type c), however, as the temperature is increased, the drawing behaviour moves from (type c) to (type b) and
finally to (type a). At very high temperature, polymer chains are highly mobile and are able to deform easily with high relaxation
rates. A moderate temperature where enough stresses could be built that can initiate a neck drawing with a well defined natural
draw region is most preferred route. Therefore the drawing temperature of a filament is determined where good natural draw is
obtained with neck formation.
(b) Effect of rate of drawing: Rate of drawing at a constant temperature has an opposite effect. As the rate of drawing is low,
polymer has enough time to relax from the drawing stresses and shows flow deformation behaviour (type a). As the rate of
drawing is increased, the material is able to draw through the formation of a neck (type b). At very high rates, the material may
not be able to relax at all and the built up of elastic stresses leads to a brittle failure (curve type c).
Therefore, if we need to draw a material at a very fast rate, which is true for modern high production machines, the temperature
of drawing would need to be raised substantially to get desirable neck drawing.
(c) Effect of starting material: Starting material may also have great influence on the kind of draw the fibre would undergo. In
purely amorphous materials, it is often said that the cold drawing (neck drawing) occurs at temperatures that are a little below
the glass transition temperature. However, in semicrystalline materials the necking phenomena can occur at temperatures above
the glass transition temperature.
If the fibre is highly crystalline or highly oriented, the fibre may show a brittle failure (type a). A highly amorphous material is able
to undergo neck drawing if it can crystallize. A purely amorphous material without any tendency to crystallize will only show flow
deformation behaviour and will break eventually by thinning down
(d) Effect of moisture/plasticizers content: The presence of plasticizers or even moisture may change behaviour of the
drawing material. Presence of plasticizer lowers the build up of elastic stresses and the material may show more of flow
deformation behaviour. Nylon-6 is more sensitive to moisture content and therefore shows flow deformation drawing (type a) at
higher moisture content. Solution spun fibres with traces of solvent, which have already undergone crystallization (such as wet
spun acrylic fibres) show only flow deformation type drawing (type a). Such structures lock, when the T of the drawn fibre is
g

pushed to a high temperature as the solvent is removed from it on subsequent washing.


Optimization of parameters
Formation of a stable neck is the most important criteria to decide that a good drawing is being carried out. The angle of neck is
related to the level of internal stresses. Higher the internal stresses, sharper is the angle of necking. Necking can also be related
to the birefringence of the drawn fibre, as internal stress alone dictates the level of orientation of the polymer chains. However, if
the angle of neck is too sharp, the drawing may prove to be difficult and unstable. Higher draw ratio, higher extension rate, and
low temperature all lead to higher angle of neck. At very high necking angle, the fibre may develop defects such as internal
cracks and fissures. This may give opaque appearance to the fibre. Therefore, fibre should be drawn just short of when such
defects start to appear. This defines the maximum extent ( ) to which a fibre may be safely and usefully drawn. This may
max max

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
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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.
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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

network draw ratio according to equation [4].

-----[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

drawn yarns as a function of draw ratio


The amorphous and crystalline orientation factors are plotted as a function of draw ratio in Figure.4.9 . The crystalline orientation
factor f initially increases sharply, leveling off at higher draw ratio,whereas f initially rises very slowly becoming important only at
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.

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