MODULE 1 HIGH - PERFORMANCE AND SPECIALITY FIBRES

1.1 Introduction, Classification and Developments (2 Lectures)

This chapter introduces the high-performance fibres and speciality fibres. The classification and
developments of these fibres are briefly discussed.
How are High-Performance and Speciality Fibres different from commodity fibres ?
Commodity fibres or general purpose fibres are typically used in a highly competitive price
environment which translates into large scale high volume programs in order to compensate for the
(often) low margins.
Conversely, high performance and speciality fibres are driven by special technical functions that
require specific performance properties unique to these fibres.

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.

Most high-performance fibres have high tensile modulus and strength. Many of them are also known
for their thermal resistance; they do not catch fire and provide protection against heat. Therefore,
fabrics constructed from these fibres can be used for applications where protection against fire is
required.
Similarly, for certain applications, resistance against chemicals is desired.
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).
Need?
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
Strong demands on good performance properties -such as strength/modulus, durability and
dimensional stability and on functions such as flame-retardancy, hydrophilicity, hydrophobicity,
biocompatibility, smart and responsive textiles, sensors, etc. Figure 1 shows the applications of high
performance and speciality fibres for different end-uses.

Mooring & towing

Gloves

Trilobal fibre: for high lusture

 Nanofibre: with high surface to volume ratio

Figure 1. Applications of High Performance Fibres

Classification of High Performance Fibres
i) Based on the performance properties:

These are generally characterized by remarkably high values of:

1. Tensile strength and modulus
2. Resistance to heat, flame
3. Resistance to chemical agents that normally degrade conventional fibres

Figure 2. The step change in strength and stiffness from first generation to second generation
manufactured fibres and pointer showing different generations of textile fibres
As shown in Figure 2 , 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 inFigure 3. Such materials can be used for artificial muscles, sensors
and actuators etc.
 Figure 3. Animation showing stimuli sensitive fibre
ii)Based on the nature of bonding:

Based upon the nature of bonding, these can be divided into three main categories:
The high performance fibres possess a strong and continuous axial bonding.
Linear polymers : These polymers belonging to this group are one-dimensional and have a very high
aspect ratio. Aramids, gel-spun PE, thermotropic polyesters, PBO 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. As shown below, the attempt is to obtain an ideal extended chain
conformation of linear polymers with reduced/no defects in the structure. Theoretical moduli of ~100
GPa were calculated in the direction of primary bonds, but only ~0.5 GPa when controlled by Vander
Waals bonds.
 Figure 4. Ideal extended chain structure
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.
The deformation of such a system during solidification would result in highly oriented structure. The
chemical structure of some rigid polymers suitable for producing high performance fibres are shown
in Figure 5.

Figure 5. Chemical structures of rigid polymers

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. As shown
in Figure 6 these fibres have strong covalent bonds in the axial direction of fibre and weak
intermolecular bonding in transverse direction.
 Figure 6. Strong axial covalent bonds and weak transverse intermolecular bonding
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 (Figure 7).

Figure 7. 2-Dimensional Graphitic Sheets of Carbon Fibre

Three-Dimensional Networks : Trifunctional or multifunctional precursors/monomers can be used to
derive three-dimensional (3D) networks (Figure 8). Such networks in the fibre form are the basis of
thermoset, glass and ceramic fibres.

a) b)
Figure 8. 3D- Network materials: (a) A crystalline network in a ceramic fibre; (b) An
amorphous network as in glass.
Generally, these polymeric fibres have strength, stiffness and breaking extensions comparable to
conventional textile fibres. Strong intermolecular bonding gives thermal resistance and the inert
molecular structure impart chemical resistance in these fibres. The three-dimensional inorganic
networks, such as those constituting ceramic and glass fibre also possess high thermal resistance.
High performance fibres can be used for reinforcement of composites to enhance their performance
properties. The following example can illustrate how the uniaxially oriented glass fibre in polyester
resin can enhance the modulus by nearly 10 times.

Glass fibre reinforced polyester composite:

Example: Uniaxially oriented glass fibre in polyester resin as shown in Figure 9 below.

The reinforced composite prepared using

40% Glass fibres (Vg)

60% Polyester resin (Vr)

Modulus of glass fibre (Eg) = 69 GPa,

Modulus of polyester resin used for the matrix ( Em) = 3.4 GPa
 Figure 9. Schematic of unidirectional glass fibre
reinforced composite
E = Ef. Vf + Em . Vm
Longitudinal modulus of elasticity = 69 x 0.4+ 3.4 x 0.6 = 30 GPa
Fibre load (Ff) / Matrix load (Fm) = σg .Ag / σr .Ar
= Ef. Vf / Em . Vm =69x 0.4 / 3.4 x 0.6 or Ff / Fm = 13.5

Copyright IIT Delhi © 2009-2011. All rights reserved.

MODULE 2. HIGH STRENGTH HIGH MODULUS FIBRES

 2.1 Aramids: Polymerization, Spinning and Properties (3 Lectures)
amid” is short for “aromatic polyamide".
the Federal Trade Commission the definition for aramid fibre is:
ured fibre in which the fibre-forming substance is a long-chain synthetic polyamide in which at least
mide (-CO-NH-) linkages are attached directly between two aromatic rings”.
have much superior mechanical properties than steel and glass fibres on an equal weight basis, and maintai
high temperatures. Due to these properties, they are replacing metal wires and inorganic fibres in some hig
applications and are widely used in areas like protective clothing for hostile environment where heat, chem
present. By definition, the aramid family will cover Kevlar, Nomex, Technora, Teijinconex, Twaron etc fib
hese 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

ion of Aramids
elt polycondensation methods for the preparation of aliphatic polyamides are not suitable for the
of high molecular weight aromatic polyamides because of the reduced reactivity of aromatic
d the high melting point of the resulting polymers. Aramids have a very high melting point ~ 500 ºC
before they melt. These are generally prepared by low temperature solution polycondensation of
atic amines and diacids or diacid chlorides. The polymerization medium is an inert solvent for at least
actant and solvent or swelling agent for the polymer (preferably a solvent to allow the completion of
on). The preferred solvents are dimethyl acetamide (DMAc), N-methyl-2-pyrrolidone (NMP),
phosphoric triamide (HMPA), tetramethyl urea (TMU). But no organic solvent is sufficiently powerful
o keep the polymer in solution as its molecular weight builds up. However, by addition of lithium or
ride the solvating power of many organic solvents is greatly increased. These metal halides apparently
polarity of substituted amide solvents by complexing with carbonyl group (Figure 1).

Figure 1. Interaction of metal halides with amide solvents

poly-m-phenylene isophthalamide, produced using m-phenylene diamine and dichloride of m-
cid was the earliest representative of this class and was commercialized as Nomex® aramid fibre. The
ctions occurring during the synthesis of PPTA, produced from p-phenylene diamine and –terephthaloyl
shown in Figure 2.

nylene diamine, TCL Terephthaloyl chloride, HMPA - Hexamethylphosphoramide, NMP - N-

idone

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

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

iometry
nt composition
erature
ant concentration
g

a suitable solvent gelation can be delayed until high molecular weight is reached. The balance
-Concentration-Temperature, control the solvent distribution in monomer and polymer phases and
ke the choice of solvent critical.

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

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

nthesis pathways using aromatic carboxylic acids and diamines have been investigated since diacids are
heap starting material. The reaction with triaryl phosphates in NMP/pyridine proceeds by the
hown in Figure 3.
 Figure 3. Synthesis of PPD-T polymer
ation
ng rigid macromolecules have low solubility in common solvent systems. This is because the entropy
Gibbs energy of solvation makes a very small contribution because of the rigidity. Consequently, the
f such rigid polymers achieved because of an extensive interaction of the polymer chains with solvent
hich is manifest in the enthalpy contribution to the solvation free energy. Aramids decompose before
lting, hence are spun from solution. Although both dry and wet spinning techniques are suitable, the
perties vary depending on the polymer structure and method employed.

ure

amid molecular structures, such as PBA and PPD-T are Nematic liquid crystals
quid crystal state is a distinct phase between the crystalline (solid) and isotropic (liquid) states
ular bundles (mesogens) point along a common axis, called the director

rtain favourable conditions of solvent, concentration and molecular weight, the molecules form nematic
s, i.e., they are organized in essentially parallel arrays Figure 4.

(a). Nematic Liquid Crystals 4(b). Representation of bundles of liquid crystal domains in dope
y of PPD-T in 100% sulphuric acid as a function of concentration (for two different molecular weights)
Figure 5(a). As the concentration increases, there is a rapid increase in viscosity of polymer solution
al concentration” is reached, after which the viscosity rapidly drops. The increase is the expected rise
with concentration for an isotropic polymer, the critical concentration marks the start of nematic phase
d the viscosity drop shows low-viscosity behaviour of nematic liquid crystals. The critical polymer
n needed for mesophase formation is dependent on the molecular weight of the polymer and
of solution . Such behaviour is particularly useful since it allows the preparation of dopes containing
gh proportions of polymer suitable for spinning. Figure 5(b) shows the orientation of bundles of rod
es of PPD-T with respect to the director .
 Figure 5(a). Viscosity variation of PPD-T with concentration

Figure 5(b). Representation of PPD-T liquid Crystal solution

spinning process, high molecular weight polymer, high polymer concentration in the dope and low
y are required for obtaining good mechanical properties, easy processability and low cost. Figure 6,
e diagram for PPD-T in 100% sulphuric acid. In the high concentration (18-23% PPD-T), the dope is
bout 80 °C. These dopes require to be melted before spinning and for low temperature coagulation they
to be dry-jet-wet spun. The process is best described as melt spinning of PPD-T is nematic phase, with
ating in the air gap and the acid stripped off in the coagulation bath. It is also evident from the phase
up to concentrations of 10%, dope viscosity remains low and such dopes can be wet spun.
 Figure 6. Phase Diagram for PPD-T solution in 100% sulphuric acid.
nning

wet spinning method can be used, however the much improved properties are achieved using dry-jet-wet
hnique. The anisotropic polymer dope (in concentrated sulphuric acid) is extruded through spinnerets at
C through about 1 cm air gap into cold water or dilute sulphuric acid held at about 4 °C. The fibre
n the air gap and the acid is removed in the coagulation bath. In this way very different dope and
mperatures may be used. The spinneret capillary and air gap cause rotation and alignment of domains
ighly crystalline and oriented as-spun fibres (Figure 7). When the anisotropic solutions passes
apillary hole, the capillary shear causes some of the liquid crystal domains to orient along the direction
wever, at the capillary exit, some disorientation of liquid crystal domain occurs because of die swell
disorientation is quickly overcome by filament attenuation under spinning tension. Under the conditions
al flow encountered during extrusion, the degree of parallization of nematic domains becomes very
re is highly oriented and does not require a subsequent drawing process, as is required for conventional
PPD-T fibres tend to possess superior tensile properties to those exhibited by conventional fibres. The
ament, after washing, neutralization and drying results in highly crystalline, high strength, high
e. The isotropic solution, spun by wet spinning is exposed to the coagulant as soon as it exits the
zzle, preventing the solution from complete attenuation and hence results in low tenacity, intermediate
high elongation. Using dry-jet wet spinning radial crystalline orientation as shown in Figure 8(b) is
 Figure 7. Schematic of Domain Directions in Fibre Spinning

chematic of Crystalline Orientation of para-aramid fibre: (a) random; (b) radial; (c) tangential.
Treatment
and tensile properties of as-spun aramid fibres can be further improved by heat treatment under
effect of heat treatment on the fibres spun by different techniques is shown in Figure 9. In wet spun
enacity and modulus increase exponentially with increasing temperature (and draw ratio). The effective
ns at about 360 °C and the properties attain a maximum at about 550 °C (Tm of polymer). It is
the heat treatments promote molecular chain displacement, thus allowing the formation of regular
 g between highly oriented regions of crystalline order. The wet spun yarns show major increase in
structure perfection, and orientation. In dry jet spun yarns, a jump in modulus is observed essentially
of temperature at temperatures greater than about 200 °C. The final modulus level is a function of
odulus (or orientation), with tenacity remaining constant. A moderate increase in the structural
s also indicated by density increase.

Figure 9. Effect of Heat-treatment on Fibre Properties

roperties and Possible Applications
al properties of aramid fibres, particularly tensile properties are related to the fibre structure at
vel. The polymer chain conformation and rigidity, crystalline orientation and crystallinity are the key
verning the final fibre properties. Due to the specific molecular geometry of para-aramid, i.e. Kevlar
icted tensile modulus is 200GPa and the actual value is around 145GPa. The corresponding value for
s is 127 GPa. The physical properties of some commercial aramids are shown in Table 1.
Table 1. Properties of some Aramids Fibres
 ure

T solution are extruded through a spinneret and drawn through an air gap during fibre manufacture, the
line domains can orient and align in flow direction. Thus aramids can acquire a high degree of
long straight polymer chains parallel to fibre axis. This is a distinctive feature of the PPT molecule,
ved from the bonding of rigid phenylene rings in the para position. The occurrence of amide groups at
vals along the linear chain facilitate extensive hydrogen bonding and this leads to a high degree of
confirmed by wide angle X-ray and electron diffraction patterns of Kevlar fibres. The extruded material
es a fibrillar structure. Kevlar fibre contains several levels of superimposed microscopic and
c structures including the crystal lattice (Figure 10), pleated structure, fibrillar structure and
ructure. When a polymer is spun from highly concentrated anisotropic ,the chains form an essentially
(pseudo–orthorhombic ) unit cell of dimensions shown in the figure below. There are two molecules
and two monomeric units in axial repeat, resulting in a crystallographic density of 1.48 g cm-3. Fibres
dopes containing relatively low concentrations of polymer exhibit a slightly different packing
lateral displacement (b/2) of chains along alternate (200) planes. Both modifications are present in
un from intermediate concentrations. The average lateral crystallite size is of the order of 5-6 nm.
 Figure 10. Crystal Lattice of Kevlar Fibre
ectron diffraction and dark field transmission electron microscopy of PPD-T point to an unusual radial
f hydrogen bonded sheets and pleated structure (Figure 11). The pleats are around 500 nm long with
mponents of pleat being at approximately equal but opposite angles of 170°. This results in a variation
y of 5°. Narrow bands of 30 nm width spaced at intervals of 250 nm and 500 nm are resulted from the
nges in crystalline orientation. It has been suggested that the pleating results from the viscoelastic
liquid crystals which shrink elastically after release of stretching during fibre formation. Because
id crystals have sufficiently long relaxation times, the zig-zag structures produced in the dope by
main in fibres after solidification.

Figure 11. Radial pleated structure model of PPTA fibre

columns (Figure 12), which are aggregates of elongated, oriented liquid crystalline domains lie along
ats. The surface microstructure observed by atomic force microscopy reveals that many pleats are
bre axis direction. The polymer chain orientation angle obtained from azimuthal x-ray diffraction is
for Kevlar 29 and < 12° for Kevlar 49.

Figure 12. Fibrillar structural model of PPD-T fibre

xhibits skin-core differentiation in several ways. Kevlar filaments are not dyeable, but damaged fibres
bre are accessible to dye to some extent. Microscopic examination showed that the dye found selective
fibre core either from the fibre ends or through cracks in the damaged fibre skin. The skin exhibits a
uous structural integrity in fibre direction than the core, and the thickness of the skin is less than 1µm.

crystalline structures can be influenced by several parameters such as fibre manufacturing conditions,
nt and absorbed water. PPD-T is highly crystalline, crystallinity varies from 68-85% for Kevlar 29 and
Kevlar 49. The extended polymer chains in the fibre-axis direction leads to stiff, rigid molecules that
gh longitudinal modulus of elasticity. The aromatic ring, as well as the conjugation of electrons
terial high thermal stability, chemical stability and mechanical stiffness. The hydrogen bonds in
 se direction and covalent bonds in the fibre axis direction lead to a great mechanical property

a (HM-50) fibre, produced from a copolymer also shows a high degree of orientation and some three-
order which is not as extensive as that observed in PPD-T.

rties

s are characterized by medium-to-ultrahigh strength, medium-to-low elongation and moderately high-

modulus with the densities for crystalline fibres ranging from 1.35 to 1.45 g/cm3. Fibres of low
MPD-I (eg Nomex) have a density of 1.35 g/cm3. Fibres from PPD-T (eg Kevlar) have a density of ~

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

roperties

ilicity of amide linkage leads to moisture absorption by all aramids. In addition to chemical
fibre structure also plays a critical role in determining the moisture absorption. Different Kevlar
orb moisture to different extent. Water molecules are considered to be absorbed by the amide groups at
ds, intrafibrillar lattice deficits, inner surfaces of the microvoids to form small water clusters at low
ure.

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

s are exceedingly difficult to dye by conventional methods due to their very high Tg. The aromatic
ramid is responsible for a substantial absorption of UV light, which in turn leads to a change of colour
ive reactions as well as drop in fibre properties.

operties

s do not melt in the conventional sense because decomposition occurs simultaneously. Pyrolysis of
ylene terephthalamide) fibre leads to products p-phenylene diamine, aniline, benzonitrile etc. indicating
cleavage of amide bond. The differential scanning calorimetry studies of PPD-T reveals moisture
about 100°C, followed by melting and chemical decomposition at 500-575°C. Some aramid fibres such
hrink away from a high heat source or from a flame. Aramid fibres characteristically burn only with
cause of high LOI values. Burning produces a thick char that acts as a thermal barrier.

sociation energies of C-C and C-N bonds in the main chain are significantly higher in aromatic
han those in aliphatic ones, which gives higher thermal stability to aromatic materials. So, p-phenylene
ide is stable upto 550 °C. Excellent thermostability of poly(p-phenylene benzobisthiazole) is due to its
c character and highly rigid molecule. Introduction of flexible groups such as -O- into main chain (as
leads to a more flexible chains and lower thermal stability.

d of the amide group in poly (p-phenylene terephthalamide) has a double bond character. The
between the amide groups and the aromatic ring in p-aramids is responsible for the yellow colour and
ain rigidity which help into excellent retention of physical properties at elevated temperature.

Properties

s-strain curve of Kevlar aramid yarn as compared to other industrial filament yarns is shown
3. These curves show that Kevlar yarn has a tenacity of 22 gpd, which is more than 5 times that of steel
ce that of nylon, polyester or glass fibre. Kevlar shows an unusually high initial modulus of 475 gpd,
ce that of steel wire and fibre glass. As a spun fibre Kevlar 29 has a modulus of 62 GPa. Heat treatment
n increases crystalline orientation. The resulting fibre, Kevlar 29 has a modulus of 131 GPa. The
high strength of Kevlar can be attributed to:

matic nature and amide group.

rystallinity and orientation.
dual polymer strands of Kevlar are held together by H-bonds that form between the polar amide groups
acent chain. The mechanical properties of Kevlar are also shown in Figure 14.
omatic components of Kevlar polymers have a radial (spoke-like) orientation, which gives a high
of symmetry and regularity to the internal structure of the fibres. This is confirmed by bright
oton radiation (XANES image). This crystalline-like regularity is the largest contributing factor in the
th of Kevlar. Allen et al. have introduced the concept of asymptotic modulus as a measure of
ation and related it to the pleated morphology of the fibre.
 Figure 13. Stress-strain behaviour of aramids in comparison to other fibres

Figure 14. Mechanical properties of aramids

ted to axial compression or severe bending it shows nonlinear plastic deformation. The fibre exhibits a
a compressive strain of 0.3-0.5%. This corresponds to formation of structural defects known as Kink
60° to the fibre axis). These bands are related to compressive buckling of the aramid molecules by
tation of the amide C-N bond, which in turn reflects weak lateral properties of these highly anisotropic
 viour of aramid is also dependent on the mode of fibre deformation (tension vs. compression). With
ue no failure is observed even at loads as high as 60% of breaking strength and 107 cycles. Tensile
es at the fibril ends and propagates via shear failure between the fibrils. Skin-core gradient in the fibre
niform load sharing and hence reduces strength. However, compressive fatigue of organic high
fibres is significantly worse. The retention of tensile strength decreases with increased compressive
% strain no strength loss is observed even after 106 cycles, while at 1% strain, loss is observed within

ylene terephthalamide) fibre exhibit very low creep even at elevated temperature. At a load of 0.5 of
d after 105 sec, creep strain for Kevlar is only 0.3%. The longer life time characteristics of high melting
mainly attributed to high activation energy of primary bond breaking. Kevlar creeps under high
ep rate is almost uniform and the amount of creep strain increases linearly with log (time).

nge of properties exhibited by aramids is the main reason for their use in diverse end applications. The
applications can be divided into two broad categories:

forcement application such as tyre cord or automotive components such as gaskets and clutch linings
vanced plastic composites, used in aircraft and aerospace equipments, military vehicles, sports goods
any others.
arel related applications, such as fire protective clothing and bullet proof vests.

amid (NomexTM) has excellent thermal resistance, good textile properties but rather poor mechanical
r high performance fibre. Its applications include protective clothing, hot gas filters, industrial coated
crims and reinforcement of rubberized belts and hoses. Its inherent dielectric strength, mechanical
d thermal stability provide high usability and reliability. The para-aramid (KevlarTM) provides unique
s of toughness, extra high tenacity and modulus and exceptional thermal stability. So end use of para-
a broad range of industrial, aerospace, military and civilian applications, which include cut, heat and
ent resistant (ballistic) apparel, hard armours, brake and transmission friction parts, reinforced tyres and
, ropes and cables, various forms of composites, filament wound pressure vessels, industrial gloves,
reinforcements etc., Kevlar 49 HS(High strength) is prepared by Du Pont’s New Fibre Technology in
is specifically intended for filament winding applications and has a tensile strength 25% higher than
ard Kevlar 49, giving it a combination of high strength, low weight and good impact resistance. This
ent wound composite cylinders to be used for higher pressure duties, such as oxygen and industrial gas
ank, rocket motor casings, electrical switch gear devices and off-shore flexible pipes. Other
containing combination of meta and para substituted monomers have been developed for optimum
While each application has its specific requirements, almost all of them characteristically utilize high
h modulus, high toughness, thermal and dimensional stability, low creep, and light weight of these
arious applications are shown in Table 2.
 Table 2. Applications of Different Aramid Fibres

MODULE 2. HIGH STRENGTH HIGH MODULUS FIBRES

 2.2 Other Rigid Rod Polymers such as PBZT, PBO, PBI (2 Lectures)
s based on Aromatic Heterocyclic Polymers
undamental science of structure-property relationship developed in aramids has been further
ded to form heterocyclic rigid rod polymers. In these polymers, the structures are even more
han those of p-aramids and pose greater difficulty in processing.
fication:
ocyclic rigid-rod polymers can be classified into three categories
Polybenzazole
Polybenzimidazole
Polypyridobisimidazole

own below in Figure 1, polybenzazole polymers abbreviated as (PBX) include

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

Figure 1. Structures of PBT & PBO

enzimidazole (PBI) fibre was commercialized for its thermal stability in 1983 by Celanese.
recently, the poly(2,6-diimidazo(4,5-b:4,5-e) pyridinylene-1,4(2,5-dihydroxy-) phenylene)
), a member of polypyridobisimidazole class, was synthesized shown in Figure 2.
 Figure 2. Poly(2,6- pyridinylene-1,4 (2,5-dihydroxy) phenylene) (PIPD) or M5
facture of Polybenzazoles
or cis-PBO is synthesized by condensation polymerization of 4,6-diamino-1,3-
nedoldihydrochloride(DABCO) with terephthalic acid (TA) at 60-80 °C, while trans-PBT is
on 2,5-diamino-1,4-benzene-dithioldihydrochloride (DABDT) and TA. Due to the high cost of
acturing of PBT, PBO fibres have become more popular. The polymerization is carried out in
phosphoric) acid (PPA) solvent and molecular weights of about 50000-100000 g/mol
ponding to about 200-400 repeat units per chain are obtained. In synthesis of PBO, PPA plays a
s a solvent as well as catalyst and dehydrating agent. The spinnable solutions are obtained
y from the polymerization mixtures.
 polymers decompose at high temperatures without melting and are soluble in very few solvent
ms due to their rigid molecular backbone. PBO is soluble in strong protonic acids such as PPA,
ne sulfonic acid (MSA), chlorosulfonic acid, and trifluoroacetic acid via backbone protonation,
weakens intermolecular interaction and facilitates dissolution. Several research groups have
d the solution properties of cis-PBO and have confirmed the high chain rigidity from the
ent value of 1.8 in the Mark–Houwink equation in MSA at 30 °C.
been reported to exist in anisotropic liquid crystal PBO phase in 100% sulphuric acid at 70 °C
ut 5.5 wt% PBO. Polymerized lyotropic liquid crystalline PBO/PPA solutions are directly spun
ut polymer precipitation and redissolution via dry jet-wet spinning technique. PBO fibres are
ed using 13-17% solid content in poly-phosphoric acid solution at 60-90 °C. The structure
d during coagulation shows a network of oriented microfibrils. Heat treatment at 450-500 °C for
inute under tension results in about eight times and 10-20% improvement in modulus and
th, respectively. Similarly after high temperature treatment, the modulus of PBT fibres exhibits
arkable improvement of 0.8-16 times while the fibre strength increases approximately by 50%.
vement in overall axial orientation, crystal perfection and lateral order lead to improved
nical properties. PBO fibres have been commercialized by Toyoba Co. Ltd., Japan under the
name Zylon.
nsile strength and modulus of PBO fibres are reported to be as high as 5.8 and 352 GPa
imental fibre), respectively. The mechanical properties of PBO fibre depend on polymer
ular weight, as well as on processing and post processing conditions.
e strength and modulus retention rates of PBO fibres have also been investigated under various
nmental conditions such as temperature, humidity, and exposure to ultraviolet and visible light.
0 °C, PBO fibre (Zylon HM) retains 75% of the room temperature modulus. However, high
rature with humidity has a drastic effect on strength. At 250 °C with saturated steam, the
th retention in PBO is below 20% of its room temperature value. Therefore, PBO fibres should
red in low RH environment. PBO tensile strength also drops sharply with UV exposure in the
stage, which indicates that the products of PBO fibre for outdoor use have to be protected from
V radiation. Exposure to visible light also affects PBO strength. For example, one month
ure to two 35 W fluorescent lamps placed 150 cm away from the sample is reported to reduce
BO fibre tensile strength to nearly 70% of its original value. The excellent chemical resistance to
s organic solvents, acids, and bases leads to high strength retention; however, the PBO staple
howed low resistance under acid and base at high temperature. Besides tensile properties, fibre
sional stability is also important for structural materials. The thermal shrinkage of PBO fibre
ot air treatment for 30 min without applying load was only about 0.2%, while under the same
ions, p-aramid and co-polyaramid exhibited about 0.5 and 0.7% shrinkage, respectively. Based
creep testing, at 60% of the failure stress, failure time of 19 years is predicted for the Zylon
bre. Abrasion resistance of PBO on metal is higher than that of aramid fibres under the same
while both the PBO and aramid exhibit much lower abrasion resistance than that of nylon or
igh molecular weight extended polyethylene.
ibres have specific values of strength and stiffness in excess of all other materials. These fibres
ave excellent thermal properties and find application in heat-resistant felt in glass industry.
g to these excellent properties, PBO fibres have vast range of applications. However, these
have poor performance under compression.
D or M5 Fibre
er to develop rigid rod polymers with good compressive properties, rigid rod like polymers with
ssibility of forming strong intermolecular hydrogen bonds are desirable. Polymerization of
6-tetra aminopyridine with 2,5-dihydroxyterephthalic acid (DHTA) can result in a polymer with
xyl groups at appropriate position to contribute to the hydrogen bond network envisioned for
ved lateral strength

an readily observe that that the structure of PIPD or M5 is similar to PBO and PBT except for
lowing 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.

merization is achieved by the synthesis of the TAP:DHTA 1:1 complex, or TD complex. This
ex is significantly more stable against oxidation than TAP phosphate and it precipitates in a
ield from the combination of (alkaline) aqueous solutions of TAP and DHTA, Na or K salt
neutralization. Polymerization by this route is fast (takes about 4– 8 h) and yields high MW
er with high consistency in relative viscosities. The polymerization consists of heating the
of TD complex in polyphosphoric acid and P2O5with a trace of tin powder in a reactor at 130 –
C, under inert conditions. The P2O5 content of the solvent system impacts the final molecular
t, and obviously only the highest purity TD complex results in formation of highest MW
ers. At 180 °C, the 18 wt% polymer is a nematic and has long relaxation times. Upon cooling it
llizes at about 110 °C; the crystallized solution melts at about 140 °C. The as polymerized
ons with molecular weight (Mw) 60000-150000 were spun using conventional air-jet wet-
ng at 180 °C into a water or dilute phosphoric acid bath.

RD patterns of solidified polymer solution in PPA showed the existence of two different crystal
e phases. The crystal solvate phase 1 in the polymer solution at room temperature changed to
l solvate phase 2 which starts at 85 °C and is completed at 115 °C. It disappears above 135 °C
nematic phase appeared. The transition from nematic phase to the crystal solvate can happen by
g. The crystallinity of crystal solvates of PPID is higher than PBO and PBT. The coagulated
ashed fibre is isolated as a crystal hydrate (as spun fibre). This transforms into a bidirectional
gen bonded structure during heat treatment process transforms this into the final high modulus
crystal structure. The as-spun fibre shows attractive mechanical properties, comparable to para-
d fibres, although the modulus is higher (about 180 GPa). The as spun fibre excels in flame
nce. The crystal-to-crystal transformation during the hot drawing leads to a much higher
us, due to a more slender effective chain and stronger interchain bonding, coupled with an
vement of the orientation.

od like polymer molecules feature internal hydrogen bonds between -O-H groups and imidazole
ms, and a network in both directions perpendicular to the rod like chains between imidazole N-H
and the O-H groups. This leads to a high shear modulus and shear strength and thus to good
essive properties of the M5 fibre. The honeycomb-like structure may explain the impact and
ge tolerance properties of M5 products
ey features of M5 are that it has a higher compressive strength than PBO or PBT, and it is more
to UV and hydrolytic action than PBO. It is reasonable to assume that the NH group contributes
greater solubility and water absorbing capability of this polymer relative to PBO or PBT.

Table 1. Provisional characterization of M5 fibre spun on the bench-scale

CHS M5 experiment
PBO
Twaron (resin (Unidirectional
Property ( toyoba
HM impregnated composite test
data)
strands) bars)
Tenacity (GPa) 3.2 3.5 5.5 4
Elongation (%) 2.9 1.5 2.5 1.2
E Modulus (GPa) 115 230 280 330
Compr. Str. (GPa) 0.58 2.1 0.4 1.6
Compr. Strain (%) 0.5 0.9 0.15 0.5
Density(g/cm3) 1.45 1.8 1.56 1.7
Water regain (%) 3.5 0 0.6 2
LOI (%O2) 29 - 68 >50
 Onset of thermal
450 800 550 530
degradation, air (°C)
Electr. Conduction (S/m) - ++ - -
Impact resistance ++ -- ++ ++
Damage tolerance + -- -e ++
Weaving props. + - + +
Knot strength (%) + -- 0 0

MODULE 5. OTHER SPECIALITY FIBRES

 5.1 Elastomeric fibre (2 Lectures)
are Elastomeric Polyurethane Fibres ?
ng to ASTM definition: ‘An elastomeric material is one which at room temperature can be stretched
edly to at least twice its original length and upon immediate release of stretch, will return with force to its
mate original length.’

stomeric fibres are required for making clothings conform to, extend with and physically support the
body. To meet the requirement of textile industry these are required as threads of 50-100 micron
er, extensibility of at least 400%, easy stretch for comfort, rapid, forceful and complete recovery, high
tensile strength for machinability, good whiteness index and dyeability.

properties can be achieved if the material is capable of existing in two states:

Relaxed/coiled state
Stretched or aligned state

led state must be above its glass transition point at room temperature. The polymer should have high
l mobility to give low modulus and rapid retraction. For rapid retraction, there must be some degree of long
ntermolecular interactions.

zed natural rubber meets these requirements. However, it has low strength, high recovery force, poor
ve stability and dyeability. Hence there was a need to develop synthetic polymers fulfilling the above
ments.

nted polyurethanes have been reported to be suitable in this category and some are suitable for textile
tions. Before we understand the segmented or elastomeric polyurethanes, let us see what are
thanes ?

m polyurethane is used to describe polymeric materials with predominant urethane linkage

[-NH-CO-O-]
res that meet the molecular requirements for rubberlike threads and are based on polyurethanes are
ized as elastomeric polyurethane fibres. Interestingly, the first polyurethane fibre spun in Germany was
elastic yarn but was an ordinary “hard” yarn, rather like nylon. It was made by reacting 1,4 butanediol with
ethylene diisocyanate, the two adding together to give the polyurethane. This polymer was entirely a
thane unlike the current elastomeric fibre.

nButane diol + hexamethylene di-isocyanate = polyurethane

meric polyurethanes are segmented polyurethanes and the word "polyurethane" describes polymers with
ant number of urethane groups, together with a variety of other structurally important functional groups,
ester, ether and urea groups.

gmented polyurethane is a block copolymer of a soft and hard segment. The soft segments are very much
and flexible than the hard segments, exhibit very low intermolecular forces, and provide the low modulus
h extensibility to fibre. On the other hand, the hard segments exhibit very high intermolecular forces which
rom rigidity, high degree of hydrogen bonding and crystallinity.

erization Chemistry
polymerization process, a high molecular weight diol (polyol) is reacted with two moles of diisocyanate to
prepolymer having isocyanate groups on both ends. The function of the diisocyanate is to convert the two
yl end groups in polyol to diisocyanate ends. But inevitably some diisocyanates link glycols and therefore
trimers etc. are formed. This chain growth can be increased by dropping the diisocyanate ratio below 2.
pped polyol or macrodiisocyanate is oligomeric with a characteristic molecular weight distribution. It
s unreacted diisocyanate, because for every diisocyanate that links two glycols, another is left unreacted.

h molecular weight diol or polyol can be either ether based or ester based depending upon the type of
groups. Polyoxytetramethylene glycol (PTMG) is an example of ether based polyol, while polyadipate and
prolactone are ester based polyols. Diphenyl methane 4,4’-diisocyanate(MDI) or toluene-2,4-
anate(TDI) is used as capping agent.

Figure 1. Polyurethane Linkages

Extension

epolymer is then reacted with a chain extender i.e. a diamine or a diol to form a high molecular weight
thane. On reaction with isocyanate group, the diamine chain extender molecule will form polyurea rigid
nts and diol chain extender molecule will form polyurethane rigid segments. This fundamental difference
n the diol and diamine extended materials leads to differences in physical properties between the two
.

ommonly used diamine chain extenders are hydrazine and ethylene diamine. The schemes below show the
xtension by formation of urea and urethane linkages.

(a)
 (b)
Figure 2. Chain extension reaction
tioned above, there is a large amount of free diisocyanate in the prepolymer. This free diisocyanate reacts
ain extenders and forms the hard segment of polyurethane. The hard segments blocks grow between the
med soft segments. The soft-segment domains are random-coiled aliphatic polyethers or co-polyesters.
e of this, the final polymer has a segmented structure comprising of both soft and hard segments. The
re of the final segmented polyurethane can be best explained by the following model.

ample of elastomeric fibre is Spandex fibre. Lycra or spandex was developed in 1959 by Dupont. It is a
mer of high molecular weight poly tetra methylene glycol or caprolactone or polyethylene adipate as soft
nt and diphenylmethane-4,4’-diisocyanate or toluene-2,4-diisocyanate as hard segment.
cal Structure of diisocyanates:
cal structure of some polyols: In general the soft segment has a very low melting point,if any,and is
on a polyether or polyester of a molecular weight of the order 1000-3000.

(-OCH CH CH CH CH -CO)
2 2 2 2 2

Polycaprolactone
cal structure of some chain extension agents:
H NCH CH NH
2 2 2 2

Ethylenediamine

H NNH
2 2

Hydrazine
 Formation :
stomeric fibres can be spun both by solution (both dry and wet) as well as melt spinning technique. The
and amount of comonomers can be selected depending upon the spinning technique to be employed. The
nning is commercially the most popularly exploited method for spinning of Spandex. The wet spinning can
ed out either by spinning of final polyurethane solution or by spinning of prepolymer.

normal wet spinning, the solution is extruded into a coagulation bath through a spinneret and after
ation, combination and fusion between the filaments take place, the fibre is wound up. The spinning of
mer is known as reaction spinning.

Figure 3. Different routes for polyurethane spinning

inning
jority of elastomeric fibres made by solution spinning are dry-spun products having a polether –urethane
re. The dry spinning dope, containing at least 25% polymer, is metered through a filter pack and
ets at the top of a vertical spinning tube at required temperature. In the presence of heated inert gas
through the cell, nearly complete removal of solvent occurs as the filaments descend through the cell and
es thinner. Unlike most synthetic fibres, these fibres are not subjected to an extensional drawing stage but
d in as-spun form. After emerging from the tube, the fibre is twisted. The twist travels upstream along the
a point in the upper part of the tube where the filaments comprising the fibre fuse together and form an
ate of filaments. This fusion is indispensible for subsequent processing of the fibre to prevent damage. The
mparted is removed by the time the fibre reaches the first roller by means of the tension of the fibre itself.
he finish oil that includes anti-tack agents is applied by contact with the finishing roller to prevent yarn
on on the package and is wound up by way of second roller. As shown in the Figure 4, the heated gas is
d perpendicular to the fibre as in melt spinning. This prevents gas turbulence and heat transfer
ions. Therefore accelerates the solvent evaporation and decreases the entanglement of fibres and denier
ions.

Figure 4. Dry spinning of polyurethane

easing the spinning speeds, the main controlling parameter is the solvent evaporation rate. Therefore, for
ing the spinning speed would require:

Methods to supply heat to evaporate solvent.

Technology to diminish tension
High speed twisting technology
High speed winding technology( low modulus so difficult to wind)

on Spinning:

tion spinning, the macro diisocyanate or the prepolymer is extruded in a bath containing chain extender.
emical reaction (chain extension) and the final filament formation occur simultaneously hence the name
on spinning”.

al filament formation and chemical reaction in the filament occur almost simultaneously. This is the second
mportant spinning process employed for spandex after dry spinning. The technique exploits the high
ty of diamines with diisocyanates. Prepolymer formed from either polyether or polyester macroglycol and
anate, mixed with pigments and stabilizers is metered through spinnerets in the coagulation bath
ing diamine. As the diamine diffuses to the surface of extrudate, chain extension reaction occurs rapidly to
gradually thickening skin of block copolymer containing urea hard segments. The fibres made in this way
ompletely reacted on leaving the diamine bath and therefore bond with one another within the multi-
t yarn structure. The product is therefore fused multi-filament yarn, in contrast to the solution spun
s.

ments are guided out of the bath before the reaction is complete (they still contain a core of fluid
mer).It is supported on a belt and cured in an oven to remove the volatiles and complete crosslinking
n. Reaction spun spandex filaments are collected in bundles at the bath exit as in wet spinning. This
offers economic advantages in polymerization and solvent recovery. However, it has a product limitation
because of the bath drag on the filaments while they are soft and not fully converted. Therefore, the
g of lighter fibres by this technique is difficult. Another limitation of this process is difficulty in controlling
al structure and molecular weight distribution.

pinning

inning of Spandex polymers is carried out on a small scale. In order to avoid degradation during melt
g process, the polymer with polyurethane linkages rather than polyurea hard segments are preferred. The
ntermolecular attractive forces in polyurethane segments result in reducing the final spinning temperature.
er, melt spun fibres can be produced from both polyether and polyester macroglycols reacted with
anate and chain extender ethylene glycol or 1,4 butane diol.

t-spinnable polymers, chain extension is carried out as described above, with two exceptions. The solvent
ed, of course, and the chain extender is a low molecular weight diol with primary hydroxyl groups (e.g,
e glycol). A basic or metalloorganic catalyst of the type described earlier is useful for accelerating the
n. Since diols are principal ingredients of both the hard and soft segments, melt-spinnable polyurethanes
produced alternatively in a single-step reaction of diisocyanate with a mixture of macroglycol and chain
er. Because of the statistical nature of the reaction, however, one-step synthesis gives a more polydisperse
opolymer with less well defined hard and soft-segment domains and poorer fibre properties.

stomeric fibres have elongation at break of over 400% with good tenacity and completely elastic recovery,
wn in Figure 5. This is in contrast to other type of stretch yarns made by ‘texturing’ or crimping a
plastic fibre,such as polyester or nylon.
 Figure 5. Elastane stress/strain curve for elastomeric fibres
ure-Property Correlation

xible soft segments comprise the predominant and continuous phase of the fibre, usually 65-90% by
In the relaxed fibre, they are essentially unoriented but uncoil and straighten to form crystalline regions
alignment. This results in stiffening and strengthening of the extended fibre. On release the soft-segment
ites melt and the chains recoil with a force derived largely from entropy change. The length and nature of
t segments determines the maximum extensibility of fibres.

ic diisocyanates condense rapidly with the other glycols and diamines without any elimination product.
ore is a preferred choice in hard-segment formation. The hard segments are commonly aromatic-aliphatic
as. The hydrogen bonded interactions between urethane groups and urea groups contribute to hard
nt domain formation. The hard segment blocks are connected to soft segments by urethane linkages.

fibre formation, the hard segments from several chains get associated into strongly bonded clusters or
nt" domains. They comprise less than 25% of the mass and form islands of a discontinuous phase and
the polymer to a three dimensional network. The main forces of attraction are hydrogen bonds between
ups and carbonyls. As mentioned above soft segments form a major fraction and this results in a easy
low modulus) and high degree of stretch.

egments affect physical properties such as modulus, hardness, tensile strength and performance at high
ature. Higher conc. of polar groups in hard segments, cause an increase in cohesive forces and hence
r physical properties. On the other hand, soft segments determine or control the elongation or stretch in
bres. Polyether based soft segments exhibit higher extension and lower physical properties than polyester
soft segments (due to weaker chain interactions). Polyethylene adipate gives high tensile strength as it
izes on extension. Increase in molecular weight of soft segment causes a decrease in modulus and increase
gation at break. Generally soft segment -60-90% by weight and hard segment <25%

Figure 6. Schematic representing hard and soft segments of elastomer

rd and soft segments are spatially separated and form discrete domains. Polyester based elastomers show
level of crystalline order compared to polyether based polyurethanes. The lower crystalline order in
er based elastomers may be attributed to the more irregular chemical structure. On extension, soft
nt polymer chains undergo stretching and disentanglement, causing rigid domains to lie in a disoriented
r. In the case of polyether based elastomers, extension ~150% results in marked elongational
ization of soft segments.

elastomer is further elongated upto 500% extension, the orientation of soft segments improves only to a
xtent, while the hard segments get oriented in the direction of elongation as the maximum loading of
n the soft segments oppose any further extension. Therefore, further extension causes a sliding process
n hard segments.

00 % extension, this process is complete and treatment of extended sample with warm water (80 °C)
in uniform distribution of forces amongst soft segment chains. This causes a loss of elongational
ization. On relaxation the soft segments disorient completely, while the hard segments tend to remain in
d form.

ious mechanisms of hydrogen bond disruption or physical relaxation in hard segments are shown
atically Figure 7.
 Figure 7. Mechanism of hard bond disruption & relaxation

in hard segments

MODULE 2. HIGH STRENGTH HIGH MODULUS FIBRES

2.5 GEL SPUN PE FIBRES (3 Lectures)
 sic Concepts for Production of Ultrahigh Strength Polyethylene (UHSPE)
Fibres
echanical properties of fibres obtained from flexible polymers like polyethylene by conventional melt
g technique, are much lower than the estimated extended chain structure based on the bond strength. As
sed, it was explained in lecture 2 (module 1), that for realizing high mechanical properties, it is essential to
ighly extended chain structure without any defects. As the chain ends are known to behave as defects, it
cted that higher molecular weight materials will have lower extent of defects resulting from chain ends.
ore, for producing the high performance polyethylene (HPPE) an ultra-high molecular weight (UHMW-PE) is
s the starting material. The ideal structure of HPPE fibres is shown in Figure 1. In this lecture, the
al requirements of producing such a structure will be discussed from the viewpoint of defect reduction.

Figure 1. Orientation of polymer chains in HPPE and regular P E

ra high molecular weight PE is a preferred starting material from point of defect reduction, however the
pinning of such a high molecular material is not possible due to the extremely high melt and elongational
ties of the melt. Secondly, the drawing of the melt processed UHMWPE is only possible to a limited extent
presence of very high degree of chain entanglements (Figure 2) per molecule. The molecular chains are
to move freely with respect to each other, and therefore, cannot be unfolded. These long molecular
cannot pass through each other in the time scale of drawing deformation. Therefore, even after
g/stretching, it is difficult to realize ideal or uniaxial extended chain structure.Figure 2, shows the concept
nglements and drawability of polymers. On the other extreme, in the dilute solution, the entanglement
y is very low, the stresses applied during spinning and drawing do not completely transfer from one chain
r chain because of poor connectivity, and the molecular chains remain in coiled or folded configuration.
nce of low entanglement density in a solution results in many molecular chains being left free in coiled
ar) conformation to begin with, and on spinning or drawing, these molecular chains are unable to orient.
sults in poor spinnability.
means that for making high performance fibres from flexible polymers, the spinning process
d be modified in such a manner that it allows formation of fully extended and oriented polymer
s.
 Figure 2. Drawability of different types of solutions
been established that for the formation of high strength fibres from flexible polymers, it is necessary to
its entanglements (extent or degree) during the spinning process. In a suitable solution, where just
nt entanglements exist between polymer chains, the spinning stresses are able to transfer to all the
without any hindrance. Such an optimum level of entanglement density is required for obtaining high
bility of polymer network. In semi-dilute solution in an appropriate solvent, the polymer molecular chains
ced into extended chain structure using physical interactions in the gel state and the morphology of the
an be controlled during the crystallization process.
spinning process, the polymer solution is prepared at temperature and conditions where it is flowable and
uded to conditions where it forms a gel structure. This allows the individual molecular chains to connect
lly with each other, and on coagulation, form a network structure which is able to undergo very high draw
o give fibre with high tensile strength and modulus. In case of polyethylene the ultra-drawing can be
d as the crystallization during drawing does not prevent drawability due to weak interactions between
er chains.

pt of Gel Spinning

spinning process, the entanglements are optimized to a number that is just sufficient to transfer the
g stress between chains. For this, one entanglement per chain has been reported to be enough. Such a
on can be realized in a solution at a critical concentration (C*), at which the random coils of single polymer
begin to overlap each other. The critical concentration C* depends on the average molecular weight (M) of
ymer and molecular weight between entanglements (Me). The entanglement molecular weight Me,
ds on the flexibility/nature of the polymer.

----------------------(1)

eans that for a particular polymer the critical concentration decreases with increase in molecular weight.
low concentration (C*), theoretical maximum drawing is possible. On the other hand if we consider the
g of a single molecule from its random coiled state the maximum attainable draw ratio can be predicted
he following relation:

-------------------(2)
c is a material constant.
 eans that the maximum attainable draw ratio increases with the molecular weight (M) of the polymer. If
awing of UHMWPE gel-like fibre is performed under such ideal concentration condition, the above argument
d good. However, for economic reasons, the actual spinning is performed at concentrations much higher
eal concentration C*.This region is called semi-dilute region.

aximum draw ratio of gel-like fibres is also related to both concentration (C) and molecular weight (M) as
below.

-------(3)

ry to equation 2 (applicable for ideal conditions), the maximum draw ratio decreases with increase of the
lar weight and concentration (for true spinning conditions). This can be explained by an increase of
lement number. Therefore, as low a concentration as possible is preferable for higher drawability (C~C*).
tical and experimental C* values for ultra-high strength polyethylene having molecular weights above
00 g/mol have been reported to be 0.5-0.7 wt%..

above argument, it is assumed that the entanglement points of semi-dilute or concentrated solutions act
manent cross-link points even after being solidified (which is not true).For a lower molecular weight
er like conventional polyethylene, the higher number of chain ends can easily pass each other through the
lement point to produce a high level of so-called disentanglement during the drawing process, which
the orientation of lower molecular weight polymers very difficult, because disentangled chain ends are
o relax to the random coil state. Even with UHMWPE, the disentanglement possibly occurs during the
g process due to crystallization, which reduces the entanglement number to some extent. Therefore, it
es necessary to use spinning concentrations higher than critical concentration. This mechanism allows
tion of UHSPE even at much higher concentration (C > C*).
Spinning Process for Polyethylene
hylene was the first polymer for which gel spinning was successfully used to produce high performance
The main reasons for this are:
the highest values of theoretical tenacity and modulus among flexible polymers
simple planar zigzag chain structure without any bulky side group
lack of high inter-molecular interactions
high crystallinity
possibility of producing ultra high molecular weight polymer

ain steps of the gel spinning process are:

Polymer dissolution to prepare a homogeneous dope
Spinning of a solution of ultra high-molecular weight polyethylene (UHMW-PE)
Gelation and crystallization of the UHMW-PE
Superdrawing and removal of the remaining solvent
 Figure 3. Process flow diagram for UHMPE fibres
gh molecular weight polyethylene with an average molecular weight of one million or more is used. Both
erage molecular weight and the molecular weight distribution are important. From the economic point of
he concentration of the solution should be as high as possible. Optimum concentrations little above the
concentration are used for obtaining high drawabilty. The solvents should exhibit good solubility of PE at
mperatures (>100 °C) but at lower temperatures (<80 °C), it should allow easy crystallization of the
er chains. After spinning, the solution is quenched in air, the solvent is removed and a gel fibre is formed.
n be done by evaporation or by extraction of the solvent. Various solvents, such as tetralin, decalin,
alene, mineral oil, paraffin oil and paraffin wax, have been reported for gel spinning of UHMWPE.
vely high-concentration polyethylene solution is prepared as uniformly as possible, because any
ogeneity is expected to cause a defect in the final fibre structure and this will reduce the final mechanical
ties of the fibres. In a typical process shown in Figure 4(Spinning of UHMWPE fibre), a screw-type
er is used for this purpose.
 Figure 4. Spinning of UHMWPE fibre

ng Process

he viewpoint of the spinning process, it is important to understand the rheological properties of UHMWPE
n. The polymer solution has unique non-Newtonian behaviour. As shown in Figure 5 at lower spinning
the extruded solution exhibits quite large die-swell, which is related to the highly elastic property of
PE solution. With increasing spinning speed, the size of the die-swell become smaller due to the stretching
the spinneret, and at much higher spinning speed, a phenomenon known as 'pull-out' is observed up to
nt breakage. This typical behaviour is due to the combination of higher elongational strength of the
n and its highly elastic property. Therefore, the flow management of such a highly elastic solution is very
ant during the spinning process.

Figure 5. Influence of spinning speed on extrudate behavior

he solution is pressed through the spinneret and the strain is applied, the molecules are forced into a
elongated form. This forms the first step in the orientation process.
 rmation or Crystallization

gel spinning process, the extruded solution is cooled by a gas or a liquid cooling medium for
ization. During the crystallization process, some of the entanglements are lost because the chain will be
angled before crystallization. Therefore, all entanglement points cannot be incorporated in the crystal and
another technical reason for the success of gel spinning even at high concentration.

h the crystallization process, the solution is solidified into a more rigid gel-like structure having dispersed
ites connected by a small number of entanglements remaining as pseudo-crosslinking points. Such a
re is ideal for the drawing.

Figure 6. Internal Morphology of solutions

ng

al properties of the fibre in the gel-spinning process are achieved in the drawing stage. The strength and
us are directly related to the draw ratio. The maximum attainable draw ratio is related to the molecular
and the concentration. The attainable draw ratio increases with decreasing concentration, however for
molecular weight there is a minimum concentration below which drawing is not possible, due to insufficient
lar overlap. The drawing behaviour is related to the number of chain-chain entanglements.

Figure 7. Drawing Process

he removal of the solvent, the fibres consist of microcrystalline crystals embedded in non-crystalline
al. In the subsequent drawing stage, the apparently random crystals and most of the non-crystalline
al is transformed into a highly crystalline, highly oriented fibre.
 mmercially feasible process, it is required that the drawing is carried out at high speeds with minimum
reakage. This means that the maximum draw ratio should be proportional to the deformation rate, which
is related to relaxation time of polymeric chains. This requirement is fulfilled, if the following relationship
molecular deformation holds good.

---------------------eq.1
v is the deformation rate and ζ is the characteristic relaxation time. If higher deformation rate (v >1/ )
plied, the molecular chain cannot relax the extra stress, and this may result in breakages. On the other
at v < 1/ , the molecular chains have more time to relax, and this to some extent makes disentanglement
e.

lue of relaxation time, is affected by the molecular structure of the as-spun fibre structure, i. e. chain
lement. Therefore relaxation time is also dependent on both the molecular weight and the concentration
owing expression.

m equation 1

r important factor which determines the drawing performance is the ease of pulling out molecular chains
he crystalline structure. This depends on the intermolecular interactions. Lower the extent of interaction
would be the drawing performance.
cture and Properties of Gel Fibre
drawing and removal of the remaining solvent gives the fibre its final properties. Lamellar crystals with
chains do not form the suitable building blocks for a strong fibre. Lamellar structures can be drawn to high
atios by chain unfolding. A nearly complete transformation of the lamellae into fibrils is obtained and thus
high strength.

Figure 8. Conversion from lamellae to fibrils

eformation rates in the spinline result in shish-kebab structure in as-spun fibres rather than lamellar
re (due to local inhomogenity).
 Figure 9. Shish-Kebab Structure

kebab morphology observed in the as-spun filaments originate from a solidification of long flow units
y developed in the polymer solution during spinning. Extended–chain crystals can form the shish and
chain structure forms the kebabs.

the drawing process, transformation from the shish-kebab structure into the microfibril structure has also
bserved as shown in the schematic diagram in Figure 10 : Model (a) represents the typical shish-kebab
re mainly observed in as spun fibre, model (c) represents the microfibril structure observed in the fibre
at a high-draw ratio, and model (b) represents intermediate state between state (a) and state (c) often
ed for the drawn fibres.

Figure 10. Fibre Morphology at different Draw-ratios

fibres are commercially available under the trade name of Dyneema and Spectra. The gel-spun fibres are
terized by a high degree of chain extension, parallel orientation greater than 95% and a high level of
inity (up to 85%). This gives the fibres their unique properties.

rformance of these fibres on weight basis is extremely high owing to the low density and good mechanical
ties. The tenacity is 10 to 15 times that of good quality steel and the modulus is second only to that of
carbon fibre grades and high modulus PBO. Like other high performance fibres, the elongation at break is
ely low, but due to the high tenacity, the energy to break is high.

minant mechanism for deformation is elastic deformation of covalent bonds. In high performance
hylene fibres, there is a high degree of crystal orientation. Most of the tensile deformation of PE crystal is
ated with angle bending of the chain. An estimate of crystal modulus of PE is 300 GPa. The HPPE fibre,
s Spectra1000, has the tensile modulus of 175 GPa. The lower value of HPPE fibres, as compared to the
ted values, is associated with slight disorientation of crystals with fibre axis and presence of amorphous
s.
igure 11. (a) Perfectly oriented fibre of infinitely long molecules subject to tensile strain e;

b) application of strain e to molecule; (c) application of strain e to repeat unit of molecule.

rformance properties of commercial HPPE fibres Dyneema and Spectra are given in table below.

Table1. Properties of Commercially available HPPE filament yarns

ations

applications are making progress, notably high performance ropes, high performance fabrics, and
cements for composites. In these applications, excellent properties such as light weight, super-high
h and modulus, good impact properties, environmental and chemical stability of UHSPE fibres is utilized.

Table 2. Properties and Applications of Aramids Fibres

bres possess a unique combination of performance properties. These fibres have high tenacity and high
us like other high performance fibres but are flexible and have a long flex life comparable with general
e polyamide and polyesters used in ropes. Dyneema and Spectra fibres have a high modulus but still are
and have a long flex life.

Figure 12. Comparison of Abrasion and Flex Life of Various Fibres

e in marine environment, HPPE fibre is an ideal material. Because of its low density ( lower than water), it
on water and is unaffected by water, sea water or UV light.
 Figure 13. Wet knot strength of different fibres

w weight and high strength of HPPE fibres make it possible to produce heavy-duty ropes with very special
teristics. HPPE ropes float on water, are flexible and have a low elongation. Thus, they are very easy to
. Abrasion resistance and fatigue are good to any standard, which is why HPPE ropes last much longer
ther ropes.

vens constructed by unidirectional layers of HPPE yarns bonded by various thermoplastic matrices (as
in Figure 14) are used in ballistic protection against bullets as this gives a far better protection at the
weight than fabrics.

Figure 14. Construction of Dyneema and Spectra Shield

Copyright IIT Delhi © 2009-2011. All rights reserved.

Copyright IIT Delhi © 2009-2011. All rights reserved.