HIGH PERFORMANCE FIBRES

As shown in Figure , the naturally available fibres, such as cotton, wool and silk have
tenacities in the range of 0.1-0.4 N/tex and initial moduli from 2 to 5 N/tex. In earlier days,
silk filament was mostly used for the demanding applications such as parachute fabric.
However, with the introduction of manufactured fibres, superior strength and modulus are
achieved. The reinforcement in automobile tyres moved from cotton cords in 1900, to a
sequence of improved rayons from 1935 to 1955, and then to nylon, polyester and steel, which
dominate the market now. A similar replacement of natural and regenerated fibres by
synthetic fibres occurred in most technical textiles. The maximum strength and moduli of
nylon and polyester fibres approaches 10 g/den ( ~1 N/tex) or 1 GPa and 3-10 GPa
respectively with breaking extensions exceeding 10%. The moderate strength along with
moderate extension in these fibres result in high work of rupture, while the good recovery
properties help in withstanding repeated high-energy shocks. These are called First
Generation Textile Materials.
In 1961, DuPont researchers spun para-aramid fibres from liquid-crystal solutions. High
orientation led to tenacities of 2 N/tex and moduli of 80 N/tex. Other polymer fibres have now
reached tenacities over 3.5 N/tex and moduli over 150 N/tex. At the Royal Aircraft
Establishment (RAE) in UK, Watt and his colleagues produced the first high-strength carbon
fibres by high-temperature processing of acrylic fibres under tension. This resulted in
tenacities up to over 5 GPa (3 N/tex) and moduli over 800 GPa (400 N/tex). The other group
of high-performance fibres are the inorganic fibres e.g. glass fibre. Strengths of glass fibres
reach 4 GPa (1.6 N/tex) and moduli 90 GPa (35 N/tex), which, on a weight basis, are less
than those of aramids. These fibres are classified as Second Generation Textile
Materials. These include - Kevlar, Nomex, Carbon, HPPE fibres. The Second Generation
Textile fibres showed a step increase in strength and stiffness. Besides there are sevaral
fibre forming materials with high thermal and chemical resistance.
But it must be noted that before the discovery of second generation fibres, some of the natural
fibres and manufactured fibres were used for technical textile applications.
Now there is a Third Generation of Fibres called SMART FIBRES with some special
physical or chemical properties, which give a new dimension to the use of textiles. A typical
example is Softswitch–fibres that become electrically conducting under pressure, or fibres that
change shape with external stimuli as shown in Figure 3. Such materials can be used for
artificial muscles, sensors and actuators etc.
 Based on the nature of bonding:
Based upon the nature of bonding, these can be divided into three main categories:
Linear polymers : These polymers belonging to this group are one-dimensional and have a very high
aspect ratio. Aramids(Lyotropic), gel-spun PE, thermotropic polyesters, PBO(ZYLON Lyotropic) etc.
are the part of this category. Ultra high molecular weight polyethylene with linear string of
covalently linked carbon atoms and hydrogen bonds in the transverse direction is a simplest case of
this class. While the other polymers such as Kevlar and rigid rod polymers have a more complicated
transverse structure containing aromatic rings and side groups.

Innovations were required to achieve such fully extended ideal structures. Two extreme of
molecular characteristics were employed to achieve the necessary structure. The two routes
used are:
1. Using rigid and interactive polymer chains
2. Using flexible and inert polymer chains

During processing, the rigid chains tend to associate as blocks of parallel chains or liquid crystals. The
polymer molecules are fully extended because the folding is difficult due to the rigidity of the chain.

PARA ARAMID

PARA ARAMID

AROMATIC POLYESTER

The alternate route of production of HM-HT fibres is based on the ease with which flexible, inert
chain-molecules can be pulled out into a fully-extended, oriented state. At molecular level, this has
been achieved by spinning of ultrahigh molecular weight polyethylene in the gel form and super
drawing of the extruded filament in the gel form to result in an highly extended structure.

Two-Dimensional Graphitic Sheets : Two dimensional molecular sheets or structures can be

obtained only by a specific geometry for the bond directions for example: hexagonal planar
network of carbon can result in graphite structure. The high temperature controlled
oxidation and carbonization of organic fibres under tension can be used to obtain strong
and stiff carbon fibres with axial orientation of graphitic sheets.
 Thre Three-Dimensional Networks : Trifunctional or multifunctional
precursors/monomers can be used to derive three-dimensional (3D) networks . Such networks
in the fibre form are the basis of thermoset, glass
and ceramic fibres.
The widely followed practice of using mechanical properties as the basis of
classification leads to the following four categories of fibres.

1. Fibres with average mechanical properties. Standard textile fibres belong to this
category for which Atlas and Mark [3] have laid down the following mechanical
property requirements: tenacity, 3-5gfden-\ elongation to break, 35%; modulus of
elasticity, 30-60gfden-1; and completely reversible elongation up to 5% strain. These
fibres also find uses in the industrial sector, e.g. as non-wovens.
2. Fibres with above average mechanical properties. Industrial fibres like tyre cords
belong to this category for which Atlas and Mark [3] have laid down the following
mechanical property requirements: tenacity, 7-8gfden-1; elongation to break, 8-15%;
modulus of elasticity, 5080 gf den -1; and a high degree of toughness.
3. Fibres with superior mechanical properties. These fibres would also come under the
general umbrella of industrial fibres and will have a tenacity of 8-20 gfden-1,
elongation to break of 5-15%, and modulus of elasticity of 80-250gfden-1• The
development of such fibres is a subject of intense research aimed at bridging the gap in
properties between fibres belonging to categories 2 and 4.
4. Fibres with outstanding mechanical properties. High performance fibres belong to
this category and, unlike the polymeric fibres belonging to the above three categories,
they can also be inorganic or metallic. The polymeric high performance fibres have a
tenacity of 15-50 gfden-l, elongation to break of 0.5-5% and modulus of elasticity of
2504000 gf den -1. The strength and modulus of the non-polymeric high performance
fibres are also very high though, because of their high density, the specific strength and
specific modulus will not be as high as for polymeric high performance 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”.
These fibres have much superior mechanical properties than steel and glass fibres on an equal
weight basis, and maintain these properties at high temperatures. Due to these properties, they
are replacing metal wires and inorganic fibres in some high performance applications and are
widely used in areas like protective clothing for hostile environment where heat, chemicals
and radiation are present. By definition, the aramid family will cover Kevlar, Nomex,
Technora, Teijinconex, Twaron etc fibres.
Like nylons these can also be classified as AB and AABB type polymers.

Aromatic AB polyamide: poly (p-benzamide)

Aromatic AABB polyamide: poly (m-phenylene isophthalamide) MPDI

poly(p-phenylene terephthalamide) PPTA or PPD-T

Polymerization of Aramids
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 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.

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 2.
PPD - p-phenylene diamine, TCL Terephthaloyl chloride, HMPA - Hexamethylphosphoramide, NMP -
N-methylpyrrolidone

Figure 2. Synthesis of p-phenylene terephthalamide (PPD-T or PPTA)

Dry-jet-wet spinning technique. The anisotropic polymer dope (in concentrated sulphuric acid) is
extruded through spinnerets at about 100 °C through about 1 cm air gap into cold water or dilute
sulphuric acid held at about 4 °C. The fibre precipitates in the air gap and the acid is removed in the
coagulation bath. In this way very different dope and coagulant temperatures maybe used.

Liquid crystals (LCs) are a state of matter which has properties between those of conventional
liquids and those of solid crystals. For instance, a liquid crystal may flow like a liquid, but its
molecules may be oriented in a crystal-like way.
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.

The viscosity of PPD-T in 100% sulphuric acid as a function of concentration

PROPERTIES

META-ARAMID

 Zig-zag molecular structure in MPDI – thus it prevents high crystallization- poorer tensile
strength.
 3.8 – 7.2 gpd tenacity, 125 gpd modulus, 25-40% breaking elongation, 1.38 g/cc, 4.5% MR.
 LOI =29%.
 Inherently flame retardant.

PARA-ARAMID

 22-26 gpd tenacity, 500-800 gpd modulus, 1.44-1.47 g/cc, 4.3% MR, 2.5 -4.4% Br.El.
 Rigid structure, Liquid Crystal Spinning.
 High Tg 370deg.

Applications
The broad range of properties exhibited by aramids is the main reason for their use in diverse
end applications. The aramid fibre applications can be divided into two broad categories:
1. In reinforcement application such as tyre cord or automotive components such as
gaskets and clutch linings and advanced plastic composites, used in aircraft and
aerospace equipments, military vehicles, sports goods and many others.
2. In apparel related applications, such as fire protective clothing and bullet proof
vests.

The para-aramid (KevlarTM) provides unique combinations of toughness, extra high tenacity and
modulus and exceptional thermal stability.

The meta-aramid (NomexTM) has excellent thermal resistance, good textile properties but rather
poor mechanical properties for high performance fibre. Its applications include protective clothing,
hot gas filters, industrial coated fabrics, felt scrims and reinforcement of rubberized belts and
hoses.

PBO – Zylon
  poly(p-phenylene benzobisoxazole) (PBZO or PBO)
 lyotropic liquid crystalline solutions.
 It has been reported to exist in anisotropic liquid crystal PBO phase in 100% sulphuric acid at
70 °C at about 5.5 wt% PBO. Polymerized lyotropic liquid crystalline PBO/PPA solutions are
directly spun without polymer precipitation and redissolution via dry jet-wet spinning
technique.
 solvent - polyphosphoric acid (PP A) ,methanesulphonic acid (MSA);
 Dry jet wet spinning.
 Following washing and drying, the fibres are heat-treated under tension in an inert
atmosphere. For the PBO fibre, heat treatment temperatures of 500-700°C with a residence
time of a few seconds to several minutes is typically used.
 Very poor UV resistance.
 42 gpd, 3.5% Br.El.,1200 gpd modulus, 1.54 gm/cc
 MR 2%
 LOI greater than 68 – Excellent thermal stability.
 Application – tennis racket, snowboard, reinforcements in composites, multilayer circuit
boards, athletic equipment and for marine applications and cables. Because of their
excellent thermal and flame resistance, they can be used as fire protection fabrics. Fabrics
made from these fibres are also excellent for ballistic protection.
 The thermal resistance of the PBO fibre is outstanding; there is only 10% weight loss after
heating in air at 300°C for 200h.

2,5-diamino-l,4-benzenedithiol dihydrochloride (DABDT) + terephthalic acid(TA)

AROMATIC POLYESTERS
  form a liquid crystalline phase over a certain temperature range in the melt. Such polymers
are called thermotropic liquid crystalline polymers.
 VECTRAN

A two-component wholly aromatic thermotropic polyester is made by melt synthesis from p-hydroxy
benzoic acid (HBA) and 2,6-hydroxy naphthoic 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

 The spinning process is similar to conventional PET melt-spinning. The thermotropic liquid
crystalline spinning melt is extruded at 280-350 °C through spinneret holes to form the yarn.
The as-spun fibres, which are 10% crystalline after quenching, are heat-treated at
temperatures of 250-300°C for several hours during which crystallinity increases to 20%.
 Applications - ropes and cables, because of their high strength, good abrasion resistance
and negligible creep; other applications are as bow strings, bicycle frames and sail cloth

UHMWPE – DYNEEMA, SPECTRA

  The only flexible chain fibre which has been commercialized as high performance fibre is
polyethylene.
 the melt spinning of such a high molecular material is not possible due to the extremely high
melt and elongational viscosities of the melt. Secondly, the drawing of the melt processed
UHMWPE is only possible to a limited extent due to presence of very high degree of chain
entanglements per molecule.
 GEL SPINNING of high MW PE – High draw ratio – greater than 10.
 spinning of approximately 5% solution of high molecular weight (approximate Mw 106) in
decalin or paraffin oil into a small air gap before entering a water bath at room temperature
to form a gel fibre with nearly all the solvent in the fibre and then drawing to draw ratios of
30-100 at 100-150°C, as the solvent leaves the fibre.
In gel spinning process, the entanglements are optimized to a number that is just sufficient to transfer the
drawing stress between chains. Such a condition can be realized in a solution at a critical concentration.
 30-35 gpd, 4% Br. El, 800-1200 gpd modulus.
 Low mp 150 deg.
 Low density- 0.97.
 Chemically inert and abrasion and fatigue resistant.
 Stable to exposure of water and sun, MR less than 0.1%.
 Applications- Sail ropes, cut resistant gloves, composites in aviation industry.

ELASTOMERIC FIBRES – Spandex, Lycra

  Polyurethane
 high elongation (300% or higher) and good recovery
 tenacity of 0.05-O.09Ntex-1 and a modulus of 0.013-0.022Ntex-1
 melt extrusion, solution dry-spinning, solution wet-spinning, and reaction spinning.
 comprise hard and soft segments.
 In reaction spinning, a 1000-3000 molecular weight polyester or polyether glycol reacts with
a diisocyanate at a molar ratio of about 1 : 2 to produce isocyanate-terminated prepolymer.
The prepolymer is extruded into a diamine bath where the diamine and the isocyanate react
and a polyurethane filament is formed.
 the material is capable of existing in two states:

o Relaxed/coiled state
o Stretched or aligned state
The coiled state must be above its glass transition point at room temperature. The polymer should have high internal
mobility to give low modulus and rapid retraction. For rapid retraction, there must be some degree of long range
intermolecular interactions.

 Applications - swimwear, stretch fabrics, hosiery, belts.

 The soft-segment domains are random-coiled aliphatic polyethers or co-polyesters.

 the hard segment of polyurethane.
 Most commonly used diamine chain extenders are hydrazine and ethylene diamine