HIGH PERFORMANCE

FIBERS (study guideline)

By
Dr S Chakraborty
The initial motivation for development of high
performance fibres came from the aerospace
industry seeking fibres for use in light but stiff, strong
and tough composite structural parts.

Following the success of nylon 66 fibre, the choice

of Du Pont scientists naturally fell on aromatic
polyamides of this type, which have a relatively
more rigid backbone.

The step change in strength and stiffness from first generation to

second generation manufactured fibres
Aromatic polyamides were first introduced in commercial applications in the early
1960s, with a meta-aramid fiber produced by DuPont as HT-1 and then under the
trade name Nomex.

This fiber, which handles similarly to normal textile apparel fibers, is characterized by its
excellent resistance to heat, as it neither melts nor ignites in normal levels of oxygen. It
is used extensively in the production of protective apparel, air filtration, thermal and
electrical insulation, as well as a substitute for asbestos.
Both meta-aramid and para-aramid fiber can be used to make aramid paper. Aramid
paper is used as electrical insulation materials and construction materials to make
honeycomb core.

Dupont made aramid paper during the 1960s, calling it Nomex paper. Yantai Metastar
Special Paper introduced an aramid paper in 2007, which is called metastar paper.
Both Dupont and Yantai Metastar make meta-aramid and para-aramid paper.
Thermodynamics versus copolymer composition, (p: e.g.
solubility, tractability, q: e .g ., crystallinity, softening point.)
 Polymer Design for Copolyamide Giving a High Modulus, High Tenacity Fiber

Objective Molecular design

Thermal stability * Wholly aromatic polyamide

* Absence of unstable linkage (urethane, urea,
alkylene, etc.)

Solubility * Copolymer with dissymmetrical units

* Inclusion of —O— , —C O — , —SO2— , etc.
* Amides rather than esters

Heat drawability * High molecular weight

* Enhanced chain flexibility by incorporating
—O —, —CO — , —SO2—, etc., into polymer chain

Dimensional stability * Rigid molecular chain

* Crystallinity by regular sequence in polymer
 Schematic drawing of a typical solution dry–wet hollow fiber spinning process.

The dimensions of the annular spinneret hole, the polymer–to–bore volumetric flow rate
ratio, and the take–up–to–initial velocity ratio (draw ratio) are the primary factors that
determine final fiber size.

Typically, the desired outer diameter is controlled by adjusting the draw ratio. The
ultimate outer–to–inner fiber radii ratio is determined by the polymer–to–bore volumetric
flow rate ratio.
High-Performance Fibres are generally characterized
by remarkably high :

• Tensile strength and modulus

• Resistance to heat and flame
• Resistance to chemical agents that normally
degrade conventional fibres.

Speciality Fibres: These fibres have selected

performance properties such as

• Dyeability
• Adhesion
• Absorbency
• Conductivity
• Flame retardancy
• Response to external stimuli ( produced from
specialty polymers)
• Special surface characteristics ( produced by
special techniques) etc.
• These can be obtained by using different approaches such as :
• Using Additives such as colorants, flame retardants, conducting fillers, antistatic
compounds, etc. during the spinning process.

• Surface Modification using chemical finishes for specific properties, such as

hydrophilicity, high absorbency, low friction, etc. or by plasma modification.

• Special Spinning Processes are used to produce different cross-section,

bicomponent, micro, nanofibres.
Bicomponent fibres are "co-extruded" with two different polymers in the cross section.
This allows the fibre to use the properties of both materials, and vastly expands the
array of possible fibre performance characteristics.

A non-circular cross-section can provide added functionality, such as unique lusture or

moisture transport.

The nanofibres have a very high surface to volume ratio and find potential
applications in tissue engineering, optoelectronic applications, protective textiles and
next generation filters.

Advanced or Special Polymeric Materials are used for making smart or responsive
fibres. These can be shape changing fibres (responsive to pH, temperature or electric
field), fibres that can store heat or chemicals and self adaptive fibres( i.e. self
tightening sutures, self-fitting shoes and medical devices).
These are required for meeting the ever increasing
applications for fibrous material in non-conventional sectors
such as

• protective clothing
• medical devices
• health care products
• automotive components
• building material
• geotextiles
• agricultural devices
• sportswear
• leisurewear
• filter media
• environmental protection
Variation of cross-sectional shape of extrudates of four polymers prepared using
noncircular spinning nozzle at various extrusion conditions
Introduction of microgrooves, microvoids and microcraters is of particular significance in
PET yarns, and yarns containing such discontinuities have been commercialized in Japan
since around 1985.

There are two main reasons for their introduction; the first is related to an increase in the
transport of penetrants like dyes, moisture, perspiration, etc., and the second to aesthetics
like enhancement of depth of colour, improved handle, silk-like effect, etc.

Achieved through blending an inorganic, organic or polymer additive of roughly 1μm size or
smaller into the base polymer, then to spin and draw to form fibres and finally to dissolve out
the additive from the surface of fibres.

For polyester fibres, the solvent application is done on woven or knitted fabrics, normally
with aqueous solution of sodium hydroxide at around 80-100 °C; this results in weight
reduction to give light fabrics.

Polyethylene glycol H(CH2CH20)nH 0.82% of yarn

dodecyl benzene sulphonate sodium salt (0.13 wt %), C12H25C6H4S03Na

24 filament, 50 denier bright polyester yarn,

Hot NaOH solution wash the soluble component can be removed to create microgrooves in
the fibres.
SUPER MICROFILAMENT YARNS and CONJUGATED BICOMPONENT YARN SPINNING

The normal melt-spinning route has been used to produce partially

oriented nylon and polyester yarns of around 0.7 denier per filament
(dpf), from which drawn yarn of around 0.5 dpf can be made.

Frequent filament breaks :

cohesive fracture occurs or
droplets form due to the surface tension of the polymer melt.

The production of super microfilaments of around 0.1 dpf or less is

through a different route which has been developed in Japan, and
involves the initial production of conjugated bicomponent filaments of
>1dpf and then splitting each filament into 10 or more filaments

Islands-in-the-sea type Toray conjugated

bicomponent filament for producing super
microfilaments.
As shown in the figure, about 16 or more microfilaments
from one type of polymer (islands) are embedded within a large
round matrix (sea) of another type of polymer. The microfilaments
can be nylon or polyester in a sea of polystyrene, for example, which
can be dissolved easily in an ordinary organic solvent (e.g.
tetrahydrofuran or toluene).
 The radial petal-like conjugated
fibre without central hole for
producing super microfilaments

conjugated fibre being split into eight triangular segments (polyester)

and a radial segment (nylon 6). The splitting is achieved either
through mechanical force impact generated by highly pressurized
water or by thermal action. Alternatively the radial segment may be
dissolved out; in the case of polyester, hot aqueous solution of
sodium hydroxide is a good solvent.

The radial petal-like conjugated filament with central

hole.
The super microfilaments have extremely low flexural rigidity and the
fabrics made from them are very light and soft. Besides being used as
suedes, air-permeable and water-repellent fabrics are also produced
from them as the dense array of thin fibres can support water droplets
as in a lotus leaf.
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
 Typical Applications:

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

 Draw ability 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

It has been observed that when polymers have varying viscosity, the lower viscosity polymer
tends to encapsulate the one with a higher viscosity. This is extremely important for sheath-
core spinning where, in the final fibre, the sheath is of lower viscosity polymer and the core
has a higher viscosity.
 Large viscosity differences between the two materials can also affect the
spinnability of the fibre as it exits the spinneret. Differences in viscosity and
position in the capillary lead to differing velocities for the two materials.

Compatibility of polymers for sheath-core spinning

The thermal and stress histories experienced by the two polymers coextruded to form a
single filament are significantly different in comparison with the corresponding single
component spinning.

The relative differences in the inherent polymer characteristics, such as solidification

temperature, activation energy of elongational viscosity, and the initial viscosity, are
found to be some of the major factors influencing the mutual interaction between the
component polymers.

When two polymers with the above-mentioned differences in their properties are
coextruded to form a single filament, the elongational stress development, and
therefore the orientation and orientation-induced crystallisation development in the
component that has higher solidification temperature, higher activation energy, and
higher initial viscosity, was found to be enhanced.
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.
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.
 Spinning of core sheath type bicomponent fibre

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 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:

o eccentric positioning of the inner polymer channel and controlling of

the supply rates of the two component polymers

o introducing a stream of single component merging with concentric

sheath-core component just before emerging from the orifice

o deformation of spun concentric fibre by passing it over a hot edge

o coating of spun fibre by passing through another polymer solution

o spinning of core polymer into a coagulation bath containing aqueous

latex of another polymer
Spinning of side by side type bicomponent fibre
Applications of bi-component fibres
 In such structures, the fi bre’s core can be prepared with a suitable low cost polymer to
deliver all of the benefit of the more expensive polymer at a material cost well below
that of a fibre made from an expensive surface polymer alone.

 Side-by-side bi-component fibres have self-crimping properties and rely on the

difference in shrinkage between the two polymers. During the fabric formation process,
if the fibres are not physically constrained, shrinkage can be induced by the application
of heat. Since the two polymers shrink at different rates, the material behaves like a
bimetallic strip and resultant shrinkage occurs.

 Freudenberg’s Evolon fabric uses segmented-pie or side-by-side bi-component fi bres,

which are formed and then fed directly to a hydroentangling unit where bonding and
splitting occur simultaneously.

 The smallest diameter fi bres, achieved through the sea-island process of bi-component
spinning, are smaller in diameter when compared to the split spinning process.

 In some of the bi-component fi bres, elastomeric material is used to achieve the self
crimping properties. Fibres manufactured from two different melting points
 are used for point-bonded non-wovens.
The applications of bi-component fibres are many, including:

1. Increased dyeability
2. Decreased flammability
3. Improved hand and lustre
4. Improved water absorption
5. Increased light and heat stability
6. Manufacture of microfibres
7. Fibres for ion exchange and separation applications
8. Improved strength and elastic recovery
Properties of Various Fibres
 Fibres based on Aromatic Heterocyclic Polymers
The fundamental science of structure-property relationship developed in aramids has been
further extended to form heterocyclic rigid rod polymers. In these polymers, the structures are
even more rigid than those of p-aramids and pose greater difficulty in processing.

Classification:
Heterocyclic rigid-rod polymers can be classified into three categories

 Polybenzazole
 Polybenzimidazole
 Polypyridobisimidazole

As shown below in Figure, polybenzazole polymers abbreviated as (PBX) include

polybenzothiazoles (PBT) and polybenzoxazoles (PBO). The term also includes some semi rigid
polymers such as poly (2,5(6)-benzoxazole)(ABPBO). The key structural feature of these two
polymers is the formation of the benzothiazole and benzoxazole ring structures.
 Ordered polymeric fibres

Two polymeric fibres which form lyotropic liquid crystalline solutions under suitable
conditions and have gained importance in the recent past due to their excellent
mechanical properties and thermal resistance are poly(p-phenylene benzobisthiazole)
(PBZT) and poly(p-phenylene benzobisoxazole) (PBZO or PBO).
Both reactions are carried out in polyphosphoric acid
(PPA) solventand molecular weights of 50000—100000
g/ mo1 are obtained, corresponding to about 200—
400 repeat units per chain. The persistence length of
trans-PBZT is around 500Å and of cis-PBO around 640
A, much higher than that of PPTA (200 A) or of
polyethylene (5.7 Å, consistent with the high rigidity of
the chain. The Mark—Houwink relationship for PBO is
[η] = 2.77 x 10-7 M1.8 in methanesulphonic acid
(MSA);the very high Mark—Houwink exponent of 1.8
also signifies high chainrigidity of the molecule. Their
dissolution requires the use of strong, protonating
acids such as PPA, MSA, etc. The critical
concentration curve for PBO is given in Fig.

Viscosity vs. concentration curve for

PBZO of inherent viscosity
1. These polymers are spun using the dry-jet wet-spinning techniquefrom a liquid
crystalline solution in PPA or MSA.

2. Water is used as the coagulant in the case of PBO/PPA solutions. Following

washing and drying, the fibres are heat-treated under tension in an inert
atmosphere.

3. For the PBO fibre, heat treatment temperatures of 500—700 °C with aresidence
time of a few seconds to several minutes is typically used.

4. In these fibres, the amorphous phase, as commonly understood in flexible chain

polymers, does not exist. While PBZT is axially disordered, PBO has three-
dimensional order.

920 MPa 27.0 MPa

Tensile Properties of PBO fibre
Tensile strength and modulus retention rates of PBO fibres have also been investigated
under various environmental conditions such as temperature, humidity, and exposure to
ultraviolet and visible light.

At 400 °C, PBO fibre (Zylon HM) retains 75% of the room temperature modulus. However,
high temperature with humidity has a drastic effect on strength. At 250 °C with saturated
steam, the strength retention in PBO is below 20% of its room temperature value.

Therefore, PBO fibres should be stored in low RH environment. PBO tensile strength also
drops sharply with UV exposure in the initial stage, which indicates that the products of
PBO fibre for outdoor use have to be protected from the UV radiation.
Some other properties of PBO fibre
Exposure to visible light also affects PBO strength. For example, one month exposure to
two 35 W fluorescent lamps placed 150 cm away from the sample is reported to
reduce the PBO fibre tensile strength to nearly 70% of its original value.

The excellent chemical resistance to various organic solvents, acids, and bases leads to
high strength retention; however, the PBO staple fibre showed low resistance under
acid and base at high temperature.

Besides tensile properties, fibre dimensional stability is also important for structural
materials. The thermal shrinkage of PBO fibre after hot air treatment for 30 min without
applying load was only about 0.2%, while under the same conditions, p-aramid and
co-polyaramid exhibited about 0.5 and 0.7% shrinkage, respectively.

Based on the creep testing, at 60% of the failure stress, failure time of 19 years is
predicted for the Zylon HM fibre.

Abrasion resistance of PBO on metal is higher than that of aramid fibres under the same
load, while both the PBO and aramid exhibit much lower abrasion resistance than that
of nylon or ultra high molecular weight extended polyethylene.
 Polybenzimidazole (PBI) fibre was commercialized for its thermal stability in
1983 by Celanese.

Polybenzimidazoles are a class of extremely heat-resistant heterocyclic thermoplastics. They

are prepared from an aromatic tetraamine and an aromatic dicarboxylic acid or a derivative
of it. A prominent example is the condensation reaction of diphenyl isophthalate and 3,3’,4,4’-
tetraaminobiphenyl at 270° C with subsequent cyclization at temperatures between 350 and
400° C in an inert atmosphere.
Applications

Polybenzimidazoles are known for their high-strength and high-temperature performance. They
find applications in many industrial fields including semiconductor, petrochemcial and
aerospace industries. Major applications include heat resistant apparels, contact seals, wafer
carriers, membranes for various separation processes, insulator bushings, and thermal isolators.
Thermotropic Aromatic Polyester
The polyester fibre, poly(ethylene terephthalate) (PET), has been extensively discussed
earlier as a very successful fibre. It is an aliphatic—aromatic polyester to which the
aromatic terephthalic acid residue confers rigidity while the glycol residue is responsible
for flexibility.

However, it has still not been possible to make high performance fibres of PET, even
when high molecular weight polymer is used. Wholly aromatic polyesters overcome this
shortcoming; they form a liquid crystalline phase over a certain temperature range in
the melt.

Such polymers are called thermotropic liquid crystalline polymers. Unfortunately, very
few of the aromatic polyesters are suitable for fibre-making because of their tendency
to degrade at higher temperatures and the poor tractability of the polymer melts.
Thermotropic Aromatic Polyester

A two-component wholly aromatic thermotropic polyester is made by melt synthesis from

p-hydroxy benzoic acid (HBA) and 2,6-hydroxynaphthoic acid (HNA); the hydroxyl groups
are acetylated to facilitate polymerization. As a result HBA is converted to p-acetoxy
benzoic acid(ABA) with a melting temperature of 230 °C, while HNA is converted to
acetoxy naphthoic acid (ANA) as shown below:

The components are taken in the desired

ratio and polymerized through
condensation to yield the polymer which
has a random sequence distribution of the
two components, as shown below:
 Mechanism of Smart Textiles

Smart Textile or Responsive Textile can be broadly classified based on the active
responses exhibited by them:

Change of Shape
Reversible or one way
Increase or decrease of dimensions, bending etc.

Storage and release

Heat
Drugs, chemicals etc.

Electronic functionality
Communication, entertainment, monitoring
Shape changing Textiles (fibres, yarns and fabrics)

Shape changing fibres, yarns and fabrics are developed using stimuli sensitive polymers
(SSPs).

These polymers show a reversible transformation from one state to another as a response
to various stimuli from the environment. These polymers are also known as smart-
polymers or intelligent-polymers.

Across the transition temperature, the linear SSP’s change from soluble (clear) to
insoluble form (turbid).

However, in the gel form they swell and deswell because of the presence of cross-links
by absorbing or releasing water.

For most applications these are generally used in the gel or cross-linked form. The
change may occur in their configuration, dimension or physical properties with a small
change in appropriate stimuli.
Among the various stimuli-sensitive polymers, the temperature-sensitive polymers are the most widely studied
polymers.

Besides the temperature stimulus, the other chemical and physical stimuli which bring about a reversible transition in
such polymers include electric field, solvent composition, light, pressure, sound, stress, magnetic field, and chemical
and bio-chemical stimuli (i.e. pH and ions).

These polymers provide a big opportunity for creating intelligent materials.

Photo series demonstrating the macroscopic SME for
two different poly(ε-caprolactone) based SMP.
Shape-memory alloys are metal compounds, which can memorise a
predetermined shape, and after being bent, stretched or otherwise mechanically
deformed they can return to this shape under certain temperature conditions.

This shape-memory effect is due to a phenomenon known as a thermoelastic

martensitic transformation, which is a reversible, diffusionless transformation
between two different crystal microstructures that occurs when a shapememory alloy is
heated or cooled beyond alloy specific transition temperatures.
These temperature dependent crystal structures or phases are called martensite
(low temperature) and austenite (high temperature)
The response temperature of shape memory is dependent on the melting
temperature of the soft segment crystals. The final recovery rate and the
recovery speed are mainly related to the stability of the hard segment domains
under stretching and are dependent on the hard segment content. Control of
hard segment content is important in determining the physical properties of
shape memory polyurethane. The amount of hard segment rich phase would
affect the ratio of the recovery, that is, the low content leads to the recovery
of the deformed specimen being incomplete
 The conventional SMP systems include cross-linked PE, PE/nylon6 graft copolymers,
trans-polyisoprene (TPI), cross-linked ethylenevinyl acetate copolymer, styrene-based
polymers, acrylatebased polymers, polynorbornene, cross-linked polycyclooctene,
epoxy-based polymers, thiol-ene-based polymers, segmented polyurethane (PU),
and segmented PU ionomers.

SMPUs are produced by commonly used polymerization methods, i.e., solution or bulk.
Cyclic, Thermomechanical Characterization
The shape-memory effect can be quantified by cyclic, thermomechanical
investigations. The measurements are performed by means of a tensile tester equipped
with a thermochamber.
The strain recovery rate Rr quantifies the ability of the
material to memorize its permanent shape

The strain fixity rate Rf is given by the ratio of the strain in the
stress-free state after the retraction of the tensile stress in the
Nth cycle εu(N) and the maximum strain εm

Thermomechanical characterisation of shape memory fibres

Polynorbornene
The polymer network keeps the original shape even above Tg in the absence of stress. Under stress the
shape is deformed and the deformed shape is fixed when cooled below Tg. Above the glass transition
temperature polymers show rubber-like behavior. The material softens abruptly above the glass transition
temperature Tg. If the chains are stretched quickly in this state and the material is rapidly cooled down
again below the glass transition temperature the polynorbornene chains can neither slip over each other
rapidly enough nor become disentangled.
It is possible to freeze the induced elastic stress within the material by rapid cooling. The shape can be
changed at will. In the glassy state the strain is frozen and the deformed shape is fixed.
Shape memory polyurethane (SMPU) is a class of polyurethane that is different from
conventional polyurethane in that these have a segmented structure and a wide range
of glass transition temperature (Tg). Segmented polyurethaneis composed of three basic
starting raw materials, these are (j) long chain polyol, (ii) diisocyanate and (iii) chain
extender. Diisocyanate and chain extender form a hard segment. On the other hand
long chain polyol is soft segment. These types of polyurethanes are characterized by a
segmented structure (block copolymer structure) and the morphology depends on
chemical composition and the chain length of the soft segment (block). The SMPU has a
microphase separated structure due to the thermodynamic incompatibility between the
hard and soft segment. Hard segments can bind themselves via hydrogen bonding and
crystallization, making the polymer solid below melting point temperature. Reverse phase
transformation of soft segment is reported to be responsible for the shape memory effect.
HIGH STRENGTH HIGH MODULUS FIBRES

Aramids: Polymerization, Spinning and Properties

The term “aramid” is short for “aromatic polyamide".

According to the Federal Trade Commission the definition for aramid fibre is:

“A manufactured fibre in which the fibre-forming substance is a long-chain synthetic polyamide in which
at least 85% of the amide (-CO-NH-) linkages are attached directly between two aromatic rings”.
Terminology and chemical structure

Aramid is a shortened form of aromatic polyamide. The term was introduced in 1972
accepted in 1974 by the Federal Trade Commission of the USA as the name of a generic
category of fiber distinct from nylon.

Para-aramids and meta-aramids

Aramids are divided into two main types according to where the linkages attach to the
rings. Numbering the carbon atoms sequentially around a ring, para-aramids have the
linkages attached at positions 1 and 4, while meta-aramids have them at positions 1 and
3. That is, the attachment points are diametrically opposite each other in para-aramids,
and two atoms apart in meta-aramids.

Structure of Twaron and Kevlar. The aromatic rings appear

as hexagons. The rings are attached alternately to either
two NH groups or two CO groups. The attachment points on
each ring are diametrically opposite each other, meaning
this is classed as a para-aramid.
Polymerization of Aramids

The usual melt polycondensation methods for the preparation of aliphatic polyamides are not suitable for the
preparation of high molecular weight aromatic polyamides because of the reduced reactivity of aromatic diamines
and the high melting point of the resulting polymers.

Polymerization of wholly aromatic polyamides is usually carried out in solution, instead of in bulk, using highly reactive diacid chlorides vs.
diacids. The reaction is fast and takes place at a much lower temperature than conventional melt polymerizations. The synthesis is
based on the familiar Scho¨tten–Baumann reaction.
Aramids have a very high melting point ~ 500 ºC and degrade before they melt. These are generally
prepared by low temperature solution polycondensation of various aromatic amines and diacids or
diacid chlorides. The polymerization medium is an inert solvent for at least one of the reactant and
solvent or swelling agent for the polymer (preferably a solvent to allow the completion of
polymerization).

The preferred solvents are dimethyl acetamide (DMAc), N-methyl-2-pyrrolidone (NMP), hexamethyl phosphoric
triamide (HMPA), tetramethyl urea (TMU). But no organic solvent is sufficiently powerful for aramids to keep the
polymer in solution as its molecular weight builds up. However, by addition of lithium or calcium chloride the solvating
power of many organic solvents is greatly increased. These metal halides apparently increase the polarity of
substituted amide solvents by complexing with carbonyl group.

Amorphous poly-m-phenylene isophthalamide, produced using m-phenylene diamine and dichloride of m-isophthalic
acid was the earliest representative of this class and was commercialized as Nomex® aramid fibre. The chemical
reactions occurring during the synthesis of PPTA, produced from p-phenylene diamine and –terephthaloyl chloride are
shown in Figure

Solubilizing Aids

Synthesis of p-phenylene terephthalamide (PPD-T or PPTA)

Interaction of metal halides with amide solvents

Poly(1,4-phenylene terephthalamide) PPD-T of high molecular weight can be prepared by low
temperature solution technique. The highest molecular weight of PPD-T was obtained in 1:2 ratio of
HMPA: NMP or 1:1.4 ratio of DMAc:HMPA and suggest salt formation which promotes PPD-T solvation.
Preparation of polymers in DMAc and NMP or mixture of these solvents (in all ratios) results in low
molecular weight polymer showing no synergistic solvent effect possibly, because no salt is formed.
Addition of salt to the mixture of DMAc-HMPA or NMP-HMPA or NMP containing dissolved CaCl2 is
preferred solvent for commercial production. During the polymerization the molecular weight increases
very rapidly within the first few seconds of reaction. The critical factors influencing polymer molecular
weight includes.

Stoichiometry
Solvent composition
Temperature
Reactant concentration
Mixing
By choosing a suitable solvent gelation can be delayed until high molecular weight is
reached. The balance of Solubility-Concentration-Temperature, control the solvent
distribution in monomer and polymer phases and therefore make the choice of solvent
critical.

PPD-T molecular weight reaches a maximum at about 0.25 m/L in HMPA/NMP (2:1
vol/vol) but in 100% HMPA, the maximum occurred at 0.7 m/L. At low concentrations,
undesirable side reactions with solvent become important to limit the molecular
weight. The drop in intrinsic viscosity at higher concentration may be ascribed to a
decrease in reactant mobility due to onset of gelation before a high intrinsic viscosity
could be attained.

At lab scale, the reaction between 1,4-phenylene diamine and terephthaloyl chloride
is best carried out by dissolving the diamine in a solvent and cooling to 0 to -15 °C. The
low initial temperature minimizes the side reactions and prevents the reaction
exotherm from overheating the mass. The acid chloride is added as a finely divided
solid with very efficient mixing. The reaction can continue in the gel state at a much
slower rate for several hours. Polymers with typical intrinsic viscosity values of 5-6 dl/g
are obtained by this method.

Alternate synthesis pathways using aromatic carboxylic acids and diamines have been
investigated since diacids are reasonably cheap starting material. The reaction with
triaryl phosphates in NMP/pyridine proceeds by the mechanism shown in Figure
 Reaction Mechanism
The first step in the condensation reaction is the attack of the amine nitrogen at the carbonyl carbon of the dicarboxylic
acid.

The local electron density at the aromatic amine nitrogen is greatly reduced by participation of the lone pair electrons
with the aromatic p-cloud, whereas the local electron density of the aliphatic counterpart is enhanced by the inductive
effect of aliphatic hydrocarbon.

This leads to a significant difference in the polycondensation reaction rate between aromatic polyamides and aliphatic
polyamides.
To compensate for reduced electron density at the amine nitrogen, the
dicarboxylic acid is activated by increasing the partial positive charge at the
carbonyl carbon. Halogen atoms (X) have proven to be effective because of
their high electronegativity.

An amide linkage is formed from the transition complex and by eliminating HX

.

Because the eliminated acid, HX, will react with the opposing amine to form a
quaternary ammonium salt, it must be removed for the polymerization to
continue.

An organic amine, such as pyridine, is often used as an acid acceptor to

regenerate the amine end. Polymerization solvents such as N,N-dimethyl
acetamide (DMAc) and N-methylpyrrolidone (NMP) are sufficiently basic to
function as acid acceptors as well.

Factors that can limit the extent of the polymerization reaction include
deactivation of chain ends, stoichiometric imbalance of reagents,
monofunctional impurities, and insufficient mobility of growing chain-ends.
Some of these factors are used to control polymer molecular weight.
Fibre Formation

Aramids being rigid macromolecules have low solubility in common solvent systems. This is
because the entropy term in the Gibbs energy of solvation makes a very small contribution
because of the rigidity. Consequently, the dissolution of such rigid polymers achieved because of
an extensive interaction of the polymer chains with solvent molecules, which is manifest in the
enthalpy contribution to the solvation free energy. Aramids decompose before or during melting,
hence are spun from solution. Although both dry and wet spinning techniques are suitable, the
ultimate properties vary depending on the polymer structure and method employed.

Dope Structure

The linear aramid molecular structures, such as PBA and PPD-T are Nematic liquid crystals

 The liquid crystal state is a distinct phase between the crystalline (solid) and isotropic (liquid)
states
 Molecular bundles (mesogens) point along a common axis, called the director

Under the certain favourable conditions of solvent, concentration and molecular weight, the
molecules form nematic liquid crystals, i.e., they are organized in essentially parallel arrays
 Representation of bundles of
Nematic Liquid Crystals liquid crystal domains in dope

Viscosity variation of PPD-T with concentration

The viscosity of PPD-T in 100% sulphuric acid as a function of
concentration (for two different molecular weights) is shown in Figure.
As the concentration increases, there is a rapid increase in viscosity of
polymer solution until a “critical concentration” is reached, after which
the viscosity rapidly drops. The increase is the expected rise in viscosity
with concentration for an isotropic polymer, the critical concentration
marks the start of nematic phase formation and the viscosity drop
shows low-viscosity behaviour of nematic liquid crystals. The critical
polymer concentration needed for mesophase formation is dependent
on the molecular weight of the polymer and temperature of solution .
Such behaviour is particularly useful since it allows the preparation of
dopes containing relatively high proportions of polymer suitable for
spinning. Figure 5(b) shows the orientation of bundles of rod like
molecules of PPD-T with respect to the director .
Highlights of Nomex Spinning:

 The polymer of inherent viscosity 1.65dlg-1 was dissolved in dimethyl formamide (DMF,
boiling point 165 DC) to give a stock solution of 20% polymer to which 4.5% lithium
chloride (LiCl) was added to improve solvent power.

 The solution was dry-spun through orifices of 0.13mm diameter into hot air at 200-210°C
and wound up at speeds of 125 m min-1.

 Alternatively it could be wet-spun by coagulating in water.

 Then the wound-up fibre was extracted in cold water for 64 h to remove LiCI-inorganic
salt and finally drawn 5.5 times its original length in steam at 56 psi pressure.

 Yarn so obtained had a tenacity of 3.6 gf den-1 and 23% elongation to break.
Liquid crystals can be divided into thermotropic, lyotropic and metallotropic phases.
Thermotropic and lyotropic liquid crystals consist mostly of organic molecules, although a
few minerals are also known. Thermotropic LCs exhibit a phase transition into the liquid-
crystal phase as temperature is changed. Lyotropic LCs exhibit phase transitions as a
function of both temperature and concentration of the liquid-crystal molecules in a solvent
(typically water). Metallotropic LCs are composed of both organic and inorganic
molecules; their liquid-crystal transition depends not only on temperature and
concentration, but also on the inorganic-organic composition ratio.
where c is the mass concentration of the polymer
(g/dL) and is the relative viscosity, which is
defined as
Fibre Heat Treatment
The physical and tensile properties of as-spun aramid fibres can be further improved by heat treatment under
tension. The effect of heat treatment on the fibres spun by different techniques is shown in Figure. In wet spun yarns,
both tenacity and modulus increase exponentially with increasing temperature (and draw ratio). The effective
increase begins at about 360 °C and the properties attain a maximum at about 550 °C (Tm of polymer). It is
probable that the heat treatments promote molecular chain displacement, thus allowing the formation of regular
chain bonding between highly oriented regions of crystalline order. The wet spun yarns show major increase in
crystallinity, structure perfection, and orientation. In dry jet spun yarns, a jump in modulus is observed essentially
independent of temperature at temperatures greater than about 200 °C. The final modulus level is a function of
precursor modulus (or orientation), with tenacity remaining constant. A moderate increase in the structural
perfections is also indicated by density increase.
Fibre Structure

When PPD-T solution are extruded through a spinneret and drawn through an air gap during fibre manufacture, the
liquid crystalline domains can orient and align in flow direction. Thus aramids can acquire a high degree of alignment
of long straight polymer chains parallel to fibre axis. This is a distinctive feature of the PPT molecule, which is derived
from the bonding of rigid phenylene rings in the para position. The occurrence of amide groups at regular intervals
along the linear chain facilitate extensive hydrogen bonding and this leads to a high degree of crystallinity confirmed
by wide angle X-ray and electron diffraction patterns of Kevlar fibres. The extruded material also possesses a fibrillar
structure. Kevlar fibre contains several levels of superimposed microscopic and macroscopic structures including the
crystal lattice (Figure), pleated structure, fibrillar structure and skin-core structure. When a polymer is spun from highly
concentrated anisotropic ,the chains form an essentially monocilinic (pseudo–orthorhombic ) unit cell of dimensions
shown in the figure below. There are two molecules per unit cell and two monomeric units in axial repeat, resulting in a
crystallographic density of 1.48 g cm-3. Fibres formed from dopes containing relatively low concentrations of polymer
exhibit a slightly different packing equivalent to lateral displacement (b/2) of chains along alternate (200) planes. Both
modifications are present in polymers spun from intermediate concentrations. The average lateral crystallite size is of
the order of 5-6 nm.

Schematic diagramof Kevlar 49 fibers showing

Studies by electron diffraction and dark field transmission
electron microscopy of PPD-T point to an unusual radial
orientation of hydrogen bonded sheets and pleated
structure (Figure). The pleats are around 500 nm long with

the radially arranged pleated sheets

adjacent components of pleat being at approximately
equal but opposite angles of 170°. This results in a variation
from linearity of 5°.

It has been suggested that the pleating results from the

viscoelastic behaviour of liquid crystals which shrink
elastically after release of stretching during fibre formation.
Because polymer liquid crystals have sufficiently long
relaxation times, the zig-zag structures produced in the
dope by shrinkage remain in fibres after solidification.
The fibrillar columns (Figure), which are aggregates of elongated, oriented liquid crystalline
domains lie along the axial pleats. The surface microstructure observed by atomic force
microscopy reveals that many pleats are parallel to fibre axis direction. The polymer chain
orientation angle obtained from azimuthal x-ray diffraction is about 12-20° for Kevlar 29 and <
12° for Kevlar 49.

Schematic representation of the microstructure of: (a) semicrystalline polymers

such as nylon 6 and (b) PPTA (fibre axis vertical).
Fibre Properties

Aramid fibres are characterized by medium-to-ultrahigh strength, medium-to-low elongation and moderately high-to-
ultra high modulus with the densities for crystalline fibres ranging from 1.35 to 1.45 g/cm3. Fibres of low orientation MPD-I
(eg Nomex) have a density of 1.35 g/cm3. Fibres from PPD-T (eg Kevlar) have a density of ~ 1.45 g/cm3.

Heat and flame-resistant aramid fibres contain a high proportion of meta-oriented phenylene rings, whereas ultra high
strength high modulus fibres contain mainly para-oriented phenylene rings.

Chemical Properties

The hydrophilicity of amide linkage leads to moisture absorption by all aramids. In addition to chemical composition,
fibre structure also plays a critical role in determining the moisture absorption. Different Kevlar products absorb moisture
to different extent. Water molecules are considered to be absorbed by the amide groups at the chain ends, intrafibrillar
lattice deficits, inner surfaces of the microvoids to form small water clusters at low vapour pressure.

PPD-T fibres show very good chemical resistance to the attack of organic solvents and aqueous salt solutions. However,
strong acids and bases do attack the fibre at elevated temperatures, causing hydrolysis of amide linkage and loss of
strength. These fibres are more resistant to acids than nylon 6,6 fibres, but not as resistant as polyester fibres, except at
elevated temperature. Resistance to strong bases is comparable to that of Nylon 6,6 fibres.

Aramid fibres are exceedingly difficult to dye by conventional methods due to their very high Tg. The aromatic nature of
p-aramid is responsible for a substantial absorption of UV light, which in turn leads to a change of colour due to oxidative
reactions as well as drop in fibre properties.
Liquid Crystal Behaviour of Polymers
Molecular architecture for liquid crystal polymers.
Criteria for melt spinnability

For a thermotropic copolyester composition to be a viable candidateas a melt

spinnable, commercial high performance fiber precursor, several criteria must be
met. These include:

Melt stability —a window must exist between the melting and decomposition
temperatures associated with the backbone molecular structure to allow for stable
processing.

Melt anisotropy—the backbone must be designed to provide the desired rheology in

the temperature range of interest, ideally between 250 and 300°C.

Molecular design—the backbone architecture must pack in thesolid state in a

manner that yields the desired solid state properties.

Monomer cost—the monomers must be cost effective when compared to

competitive raw materials and processes.
Ordered polymeric fibres
Both reactions are carried out in polyphosphoric acid (PPA) solvent and molecular weights of 50000-100000 g
mol-1 are obtained, corresponding to about 200-400 repeat units per chain. The persistence length of trans-
PBZT is around 500 A and of cis-PBO around 640 A, much higher than that of PPTA (200 A) or of polyethylene
(5.7 A), consistent with the high rigidity of the chain. The Mark-Houwink relationship for PBO is [1]] = 2.77 X 10-
7M~8 in methanesulphonic acid (MSA); the very high Mark-Houwink exponent of 1.8 also signifies high chain
rigidity of the molecule. Their dissolution requires the use of strong, protonating acids such as PPA, MSA, etc.
The critical concentration curve for PBO is given in Fig.
PBI Polybenzemidazole fibre
PBI polymer is synthesized from tetra-aminobiphenyl (TAB) and diphenylisophthalate
(DPIP). In the first stage, equimolar amounts of the monomers are heated and melted
in an inert atmosphere. As the monomers react and begin to build the PBI prepolymer,
the by-products water and phenol evolve, causing the prepolymer to foam.

After heating at 260 to 275 °C for 1–2 hours, the

foam is allowed to cool and is then crushed
into a fine powder. In the second stage, this PBI
prepolymer is heated for an additional 2–3
hours at 375–400°C to complete the
polymerization process and provide the desired
molecular weight for further processing. The
resulting PBI polymer is in the form of a fine
gold/brown powder. Solutions of PBI dope are
made by dissolving PBI polymer powder and
lithium chloride under pressure and
temperature in dimethylacetamide, DMAC, in
an inert atmosphere. A typical dope solution
contains 25% solid.
Fibre forming involves the dry extrusion of the polymer solution through a fine-holed
spinneret into a heated inert atmosphere.

As the dope solution exits the spinneret, the DMAC evaporates and the solution begins to
form into a semi-solid fibre. The resulting bundle of fibres (or ‘ends’) is drawn through a
heated chamber to complete the fibre formation and remove most of the DMAC.

The DMAC vapour is recovered through a vapour-recovery system. As individual fibre ends
exit the heated chamber, they are combined with other ends to form a sub-tow.

The sub-tows are laid and stored in a creel to await further processing. After the required
number of sub-tow creels are produced, they are brought together to form a heavy denier
tow band for final processing. This final processing, known as tow finishing, consists of five
major continuous steps:
Steps followed by spinning
(i) Washing: The tow band is run through a heated water bath to remove residual
DMAC and lithium chloride left in the fibre from spinning.

(ii) Drawing: After washing, the tow band is drawn and heated to orient the PBI fibre
and produce a final fibre denier value of 1.5.

(iii) Sulphonating: The PBI tow band is submerged in a weak solution of sulphuric acid
and subsequently heated at high temperature in an inert atmosphere to bond the
sulphur chemically to the PBI molecule. Sulphonation reduces fibre flame shrinkage to
less than 10%.

(iv) Crimping, finishing, and cutting: Depending on the customer requirements, the PBI
has finish added, is crimped and is cut to various staple
lengths, or is collected uncrimped and without finish for short-cut applications.

(v) Packaging: The finished product is packaged for delivery to the customer.
 PBI Fibre properties
Physical properties of PBI
• Flame and thermal stability
• Heat release and smoke
and gas generation
• Chemical resistance
• Physical properties
• Textile properties
Thermal stability of PBI
PBI fibre available products
 PIPD or M5 Fibre
In order to develop rigid rod polymers with good compressive properties, rigid rod like
polymers with the possibility of forming strong intermolecular hydrogen bonds are
desirable. Polymerization of 2,3,5,6-tetra aminopyridine with 2,5-dihydroxyterephthalic
acid (DHTA) can result in a polymer with hydroxyl groups at appropriate position to
contribute to the hydrogen bond network envisioned for improved lateral strength.
One can readily observe that that the structure of PIPD or M5 is similar to PBO and PBT
except for the following differences

The central aromatic ring in M5 is pyridinyl rather than benzyl

Presence of hydroxyl groups at 2-and 5-positions of diacid and
The X group in benzazole ring structure is NH.

Polymerization is achieved by the synthesis of the

TAP(tetraaminopyridine):DHTA(dihydroxyterephthalic acid) 1:1 complex, or TD complex.
This complex is significantly more stable against oxidation than TAP phosphate and it precipitates in a
high yield from the combination of (alkaline) aqueous solutions of TAP and DHTA, Na or K salt upon
neutralization.
Polymerization by this route is fast (takes about 4– 8 h) and yields high MW polymer with
high consistency in relative viscosities. The polymerization consists of heating the slurry of
TD complex in polyphosphoric acid and P2O5 with a trace of tin powder in a reactor at 130 –
140 °C, under inert conditions. The P2O5 content of the solvent system impacts the final
molecular weight, and obviously only the highest purity TD complex results in formation of
highest MW polymers. At 180°C, the 18 wt% polymer is a nematic and has long relaxation
times. Upon cooling it crystallizes at about 110 °C; the crystallized solution melts at about 140
°C. The as polymerized solutions with molecular weight (Mw) 60000-150000 were spun using
conventional air-jet wet-spinning at 180 °C into a water or dilute phosphoric acid bath.
 The XRD patterns of solidified polymer solution in PPA showed the
existence of two different crystal solvate phases. The crystal solvate phase 1
in the polymer solution at room temperature changed to crystal solvate phase
2 which starts at 85 °C and is completed at 115 °C. It disappears above 135 °C
and a nematic phase appeared. The transition from nematic phase to the
crystal solvate can happen by cooling. The crystallinity of crystal solvates of
PPID is higher than PBO and PBT. The coagulated and washed fibre is
isolated as a crystal hydrate (as spun fibre). This transforms into a
bidirectional hydrogen bonded structure during heat treatment process
transforms this into the final high modulus “M5” crystal structure. The as-
spun fibre shows attractive mechanical properties, comparable to para-
aramid fibres, although the modulus is higher (about 180 GPa). The as spun
fibre excels in flame resistance. The crystal-to-crystal transformation during
the hot drawing leads to a much higher modulus, due to a more slender
effective chain and stronger interchain bonding, coupled with an
improvement of the orientation.

The rod like polymer molecules feature internal hydrogen bonds between -O-
H groups and imidazole N atoms, and a network in both directions
perpendicular to the rod like chains between imidazole N-H atoms and the
O-H groups. This leads to a high shear modulus and shear strength and thus
to good compressive properties of the M5 fibre. The honeycomb-like
structure may explain the impact and damage tolerance properties of M5
products
Thermotropic Aromatic Polyester Fibers

To obtain high strength, high modulus fibre, it is

required to select polymer having molecular
structure in which polymer chains are packed closely
with strong bonds and low elongation. Desirable
polymers for this purpose are aromatic polyesters
comprising of highly symmetrical and rigid structure
as shown below in

However, these aromatic co-polymer have a very high melting point (are infusible) and
degrade before melting.
How to overcome this problem?

In order to lower the melting point to facilitate melt processing, it is necessary to modify the molecular
architecture. Three strategies/approaches are used for lowering the melting point.

First, one may introduce different lengths of comonomers / or aliphatic flexible groups to disturb the
ordered structure along the fibre direction. This has been done in the case of copolymers of p-
hydroxybenzoic acid (HBA)/ PET.

The copolymers of HBA/PET were among one of the first series of TLCP developed into fibres. In these
polymers, the liquid crystalline behaviour appears for compositions exceeding 30% of HBA.
p-hydroxybenzoic acid (HBA ), terephthalic acid (TA), and hydroquinone (HQ)
p-hydroxybenzoic acid (HBA), Terephthalic Acid (TA), and 4,4'- Biphenol (BP)
 Summary of preparation method and physical
p-acetoxybenzoic acid and PET characteristics of a thermotropic copolyester system based
on p-acetoxybenzoic acid and poly-(ethylene
terephthalate
Molecular architectures for promoting tractibility of
wholly aromatic polyesters.

Isothalic acid

3,4' or 4,4' functionally disubstituted diphenyl ether,

sulfide, or ketone monomers

2,6 functionally
disubstituted naphthalene monomers
2 , 6-naphthalene dicarboxylic acid (NDA),
2,6-dihydroxynaphthalene (DHN), and
6-hydroxy-2-naphthoic acid (HNA)
Hydroquinone (HQ)
Second, kinks can be designed into chemical
structures as shown below.

Third, a disturbance can be made in the lateral packing by introducing large range of
pendant groups such as in the case of p-benzenedicarboxylic acid
(TPA)/phenylhydroquinone( PHQ)/ (1-phenylethyl)hydroquinone (PEHQ).
Production of Aromatic Polyester Fibres
Commercially available TLCP fibre (Thermotropic liquid crystal polymer (TLCP) ), Vectran,
is produced from the polymer developed by Hoechst Celanese Corporation in the
1970s. The polymer is obtained by acetylation polymerization of p-hydroxybenzoic acid
(HBA) and 6-hydroxy-2-napthoic acid (HNA) and has a thermal distortion temperature of
180-240 °C and a melting point of 270 °C.
Spinning of Aromatic Polyester Fibres
The polymers with intrinsic viscosity in the range of 1.5-3 dL/g can be spun easily from their
liquid crystalline state, in a temperature range of 280°C to 360°C. The spinning process for
these thermotropic copolyesters is similar to the conventional PET melt spinning process. Upon
melting, hydrolysis and thermal decomposition of polymers occur, causing degradation of
the polymer. To minimize the decrease in intrinsic viscosity or molecular weight of the
polymer, it is necessary to dry the chips to eliminate moisture in the pellets. Flexible polymers
such as PET generally maintain their viscosity in low shear region, but in case of thermotropic
liquid crystal polymers the viscosity falls linearly as shear rate increases (even in low shear rate
region). Some type of lubricant, normally water, is applied for ease of processing. These fibres
attenuate rapidly and solidify within 10 cm from the orifice without exhibiting any ‘die swell’.
Also, no subsequent drawing is carried out. Therefore to obtain fine denier fibre, it is
necessary to either use a small diameter orifice or increase spinning draft. The as spun fibres,
which are 10% crystalline, have tenacity of about 10 g/denier, elongation of 0.2%, and initial
modulus of 425 g/denier. On heat treatment below the melting temperature (250-300 °C) for
several hours, tenacity of 23-28 g/denier is achieved, however the modulus increases only
slightly. During heat treatment, the crystallinity increases by 20% and molecular weight
increases by three times. This heat treatment time is much longer (required for solid state
polymerization) than that of a conventional heat treatment process in PET fibres because in
the melt, low molecular weight polymers are usually used in order to ease processing. TLCP
fibres are produced from polymers with varying chemical compositions. Table 1 shows
composition of liquid crystal polymers and fibre properties.
Mechanical Properties of Liquid Crystal
Fibres