Você está na página 1de 151

MODULE 1 HIGH - PERFORMANCE AND SPECIALITY FIBRES

1.1 Introduction, Classification and Developments (2 Lectures)


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

h-Performance Fibres are generally characterized by remarkably high unit

Tensile strength and modulus


Resistance to heat, flame
Resistance to chemical agents that normally degrade conventional fibres.
t high-performance fibres have high mechanical properties. Many of them are also known for their thermal resistance;
y do not catch fire and provide some protection against heat. Therefore fabrics constructed from these can be used for
ications where protection against fire is required.
ilarly for certain applications, resistance against chemicals is desired.
ciality Fibres: Fibres made from commonly available raw materials or new materials and have special performance
perties such as
Dyeability
Adhesion
Absorbency
Conductivity
Flame retardancy
Response to external stimuli ( produced from specialty polymers)
Special surface characteristics ( produced by special techniques)etc.

se can be obtained by using different approaches such as :


ng Additives such as colorants, flame retardants, conducting fillers, antistatic compounds, etc. during the spinning
cess.

face Modification using chemical finishes for specific properties, such as hydrophilicity, high absorbency, low friction,
or by plasma modification.
cial Spinning Processes are used to produce different cross-section, bicomponent micro or nanofibres.
mponent fibres are "co-extruded" with two different polymers in the cross section. This allows the fibre to use the
perties of both materials, and vastly expands the array of possible fibre performance characteristics.
odified cross-section can provide added functionality, such as unique lusture or moisture transport.
nanofibres have a very high surface to volume ratio and find potential applications in tissue engineering, optoelectroni
ications, next generation filters and protective textiles.
anced or Special Polymeric Materials are used for making smart or responsive fibres. These can be shape changin
es (responsive to pH, temperature or electric field), fibres that can store heat or chemicals and self adaptive fibres ( i.e
tightening sutures, self-fitting shoes and medical devices ).

ed?
se are required for meet/fulfil 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 and environmental protection.
Strong demands on good performance properties -such as strength/modulus, durability and dimensional stability an
on functions such as flame-retardancy, hydrophilicity, hydrophobicity, biocompatibility, smart and responsive textile
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


assification of High Performance Fibres

ased on the performance properties:

se are generally characterized by remarkably high unit

1. Tensile strength and modulus


2. Resistance to heat, flame, and
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
hown in Figure 2 , the conventional naturally available fibres, such as cotton, wool and silk have tenacities in the rang
.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
ications such as parachute fabric. However, with the introduction of manufactured fibres, superior strength and modulu
e achieved. The reinforcement in automobile tyres moved from cotton cords in 1900, to a sequence of improved rayons
m 1935 to 1955, and then to nylon, polyester and steel, which dominate the market now. A similar replacement of natu
regenerated fibres by synthetic fibres occurred in most technical textiles. The maximum strength and moduli of nylon
ester fibres approaches 10 g/den ( ~1 N/tex) or 1 GPa and 3-10 GPa respectively with breaking extensions of more th
%. The moderate strength and extension in these fibres result in high work of rupture, while the good recovery properti
in withstanding repeated high-energy shocks. These are called First Generation Textile Materials.

961, DuPont researchers spun para-aramid fibres from liquid-crystal solutions. High orientation led to tenacities of ove
ex and moduli up to 80 N/tex. Other polymer fibres have now reached tenacities over 3.5 N/tex and moduli over 150
ex. At the Royal Aircraft Establishment (RAE) in UK, Watt and his colleagues produced the first high-strength carbon fib
high-temperature processing of acrylic fibres under tension. This resulted in tenacities up to over 5 GPa (3 N/tex) and
duli over 800 GPa (400 N/tex). The other group of high-performance fibres are the inorganic fibres e.g. glass fibre.
ngths 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 th
ramids. These fibres are classified as Second Generation Textile Materials. These include - Kevlar, Nomex, Carbon,
fibres. The Second Generation Textile fibres showed a step change in strength and stiffness. Besides these ar
er fibre forming materials with high thermal and chemical resistance.
it must be noted that before the discovery of second generation fibres, some of the natural fibres and manufactured
es were used for technical textile applications.
w there is a Third Generation of Fibres called SMART FIBRES with some special physical or chemical properties, wh
a new dimension to the use of textiles. A typical example is Softswitchfibres that become electrically conducting und
ssure, or fibres that change shape with external stimuli as shown in Figure 3. Such materials can be used for sensors a
uators, artificial muscles etc.

Figure 3. Animation showing stimuli sensitive fibre


ased on the nature of bonding:
ed upon the nature of bonding, these can be divided into three main categories:

high performance fibres possess a strong and continuous axial bonding.


ear polymers : These polymeric materials of this group are one-dimensional and have a very high aspect ratio. Arami
spun PE, thermotropic polyesters, PBO etc. are the part of this category. Ultra high molecular weight polyethylene with
ar string of covalently linked carbon atoms and hydrogen bonds in the transverse direction is a simplest case of this cla
le the other polymers such as Kevlar and rigid rod polymers have a more complicated transverse structure containing
matic rings and side groups. As shown below, the attempt is to obtain an ideal extended chain conformation of linear
mers with reduced/no defects in the structure. Theoretical moduli of 11000 kg/mm2 were calculated in the direction of
mary bonds, but only 45 kg/mm2 (~0.5 GPa or N/tex) when controlled by Vander Waals bonds.

Figure 4. Ideal extended chain structure


ovations were required to achieve such fully extended ideal structures. Two extreme of molecular characteristics were
ployed to achieve the necessary structure. The two routes used are:

1. Using intrinsically rigid interactive polymer chain structure


2. Using a highly flexible and inert polymer chains
ng processing, the rigid highly interactive chains tend to associate as blocks of parallel chains or liquid crystals. The
mer molecules are naturally fully extended because the folding is difficult owing to rigidity of their structure. The
tching of such a system during solidification would result in a highly oriented structure as commercialized by Dupont. T
mical structure of some rigid polymers suitable for producing high performance fibres are shown in Figure 5.
Figure 5. Chemical structures of rigid polymers
alternate route to HM-HT fibres is based on the ease with which flexible, inert chain-molecules can be pulled out into a fully
nded, oriented state. At molecular level, this has been achieved by spinning of ultrahigh molecular weight polyethylene in th
form and super drawing of the extruded filament in the gel form to result in an highly extended structure. As shown in Figure
e 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
Graphitic Sheets : Two dimensional molecular sheets or structures can be obtained only by a specific geometry for
d directions for example: hexagonal planar network of carbon can result graphite structure. The high temperature
trolled oxidation and carbonization of organic fibres under tension can be used to obtain strong and stiff carbon fibres w
l orientation of graphitic sheets ( Figure 7).
Figure 7. 2-Dimensional Graphitic Sheets of Carbon Fibre
ee-Dimensional Networks : Trifunctional or higher precursors/monomers can be used to derive three-dimensional
) 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) An amorphous network as in glass;(b) a crystalline network in a
ceramic fibre.
erally, these polymeric fibres have strength, stiffness and breaking extensions comparable to conventional textile fibres
ng intermolecular bonding gives thermal resistance and the inert molecular structure impart chemical resistance in the
es. The three-dimensional inorganic networks, such as those constituting ceramic and glass fibre also possess high
mal resistance.

Copyright IIT Delhi 2009-2011. All rights reserved.

MODULE 2. HIGH STRENGTH HIGH MODULUS FIBRES


2.1. Aramids: Polymerization, Spinning and Properties
(3 Lectures)

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 displacing metal wires and
inorganic fibres from the market of 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

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

Figure 1. Interaction of metal halides with amide solvents


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)


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

Stoichiometry
Solvent composition
Temperature
Reactant concentration

Mixing

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

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

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

Alternate synthesis pathways using aromatic carboxylic acids and diamines have been investigated since diacids
are reasonably cheap starting material. The reaction with triaryl phosphates in NMP/pyridine proceeds by the
mechanism shown in Figure 3.

Figure 3. Synthesis of PPD-T polymer


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

Dope Structure

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

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

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

Figure 4. Nematic Liquid Crystals

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

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


For solution spinning process, high molecular weight polymer, high polymer concentration in the dope and low
dope viscosity are required for obtaining good mechanical properties, easy processability and low cost. Figure
6, shows a phase diagram for PPT-D in 100% sulphuric acid. In the high concentration (18-23% PPT-D), the
dope is solid up to about 80 C. These dopes require to be melted before spinning and for low temperature
coagulation they are required to be dry jet wet spun. The process is best described as melt spinning of PPT-D is
nematic phase, with fibre precipitating in the air gap and the acid stripped off in the coagulation bath. It is also
evident from the phase diagram that 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.
Solution Spinning

Immersion wet spinning method can be used, however the much improved properties are achieved using 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 may be used. The spinneret capillary and air gap cause rotation and
alignment of domains resulting in highly crystalline and oriented as-spun fibres (Figure 7). When the
anisotropic solutions passes through the capillary hole, the capillary shear causes some of the liquid crystal
domains to orient along the direction of shear; however, at the capillary exit, some disorientation of liquid crystal
domain occurs because of solution viscoelasticity. The disorientation is quickly overcome by filament attenuation
under spinning tension. Under the conditions of extensional flow encountered during extrusion, the degree of
parallization of nematic domains becomes so high that the product is already highly oriented without the
necessity of a subsequent drawing process, as is required for processing of conventional fibres. Thus PPT fibres
tend to possess superior tensile properties to those exhibited by conventional fibres. The attenuated filament,
after washing, neutralization and drying results in highly crystalline, high strength, high modulus fibre. The
isotropic solution, spun by wet spinning is exposed to the coagulant as soon as it exits the spinneret nozzle,
preventing the solution from complete attenuation and hence results in low tenacity, intermediate modulus and
high elongation. Using dry-jet wet spinning radial crystalline orientation as shown in Figure 8(b) is obtained.

Figure 7. Schematic of
Domain Directions in
Fibre Spinning
Figure 8. Schematic of
Crystalline Orientation of
para-aramid fibre: (a)
random; (b) radial; (c)
tangential.
Fibre Heat Treatment
The physical and tensile properties of as-spun aramid fibres can be further improved by heat treatment under
tension. The effect of heat treatment on the fibres spun by different techniques is shown in Figure 9. In wet
spun yarns both tenacity and modulus increase exponentially with increasing temperature (and draw ratio). The
effective increase begins at about 360 C (Tg of polymer) and the properties attain a maximum at about 550 C
(Tm of polymer). It is probable that the heat treatments promote molecular chain displacement, thus allowing
the formation of regular chain bonding between highly oriented regions of crystalline order. The wet spun yarns
show major increase in crystallinity, structure perfection, and orientation. In dry jet spun yarns, a jump in
modulus is observed essentially independent of temperature at temperatures greater than about 200 C. The
final modulus level is a function of precursor modulus (or orientation), with tenacity remaining constant. A
moderate increase in the structural perfections is also indicated by density increase.

Figure 9. Effect of Heat-treatment on Fibre Properties


Structure, Properties and Possible Applications
The functional properties of aramid fibres, particularly tensile properties are related to the fibre structure at
molecular level. The polymer chain conformation and rigidity, crystalline orientation and crystallinity are the key
properties governing the final fibre properties. The physical properties of some commercial aramids are shown
in Table 1.

Table 1. Properties of some Aramids Fibres


Fibre Structure

When PPD-T solution are extruded through a spinneret and drawn through an air gap during fibre manufacture,
the liquid crystalline domains can orient and align in flow direction. Thus Kevlar can acquire a high degree of
alignment of long straight polymer chains parallel to fibre axis. This is a distinctive feature of the PPT molecule,
which is derived from the bonding of rigid phenylene rings in the para position. The occurrence of amide groups
at regular intervals along the linear chain facilitate extensive hydrogen bonding and this leads to a high degree
of crystallinity confirmed by wide angle X-ray and electron diffraction patterns of Kevlar fibres. The extruded
material also possesses a fibrillar structure. Kevlar fibre contains several levels of superimposed
microscopic and macroscopic structures including the crystal lattice (Figure 10), pleated structure,
fibrillar structure and skin-core structure. When a polymer is spun from highly concentrated anisotropic ,the
chains form an essentially monocilinic (pseudoorthorhombic ) unit cell of dimensions shown in the figure below.
There are two molecules per unit cell and two monomeric units in axial repeat, resulting in a crystallographic
density of 1.48 g cm-3. Fibres formed from dopes containing relatively low concentrations of polymer exhibit a
slightly different packing equivalent to lateral displacement (b/2) of chains along alternate (200) planes. Both
modifications are present in polymers spun from intermediate concentrations. The average lateral crystallite size
is of the order of 5-6 nm.

Figure 10. Crystal Lattice of Kevlar Fibre


Studies by electron diffraction and dark field transmission electron microscopy of PPD-T point to an unusual
radial orientation of hydrogen bonded sheets and pleated structure (Figure 11). The pleats are around 500 nm
long with adjacent components of pleat being at approximately equal but opposite angles of 170. This results in
a variation from linearity of 5. Narrow bands of 30 nm width spaced at intervals of 250 nm and 500 nm are
resulted from the periodic changes in crystalline orientation. It has been suggested that the pleating results from
the viscoelastic behaviour of liquid crystals which shrink elastically after release of stretching during fibre
formation. Because polymer liquid crystals have sufficiently long relaxation times, the zig-zag structures
produced in the dope by shrinkage remain in fibres after solidification.
Figure 11. Radial pleated structure model of PPTA fibre
The fibrillar columns (Figure 12), which are aggregates of elongated, oriented liquid crystalline domains lie
along the axial pleats. The surface microstructure observed by atomic force microscopy reveals that many pleats
are parallel to fibre axis direction. The polymer chain orientation angle obtained from azimuthal x-ray diffraction
is about 12-20 for Kevlar 29 and < 12 for Kevlar 49.

Figure 12. Fibrillar structural model of PPD-T fibre


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

The surface crystalline structures can be influenced by several parameters such as fibre manufacturing
conditions, post-treatment and absorbed water. PPD-T is highly crystalline, crystallinity varies from 68-85% for
Kevlar 29 and 76-95% for Kevlar 49. The extended polymer chains in the fibre-axis direction leads to stiff, rigid
molecules that contribute high longitudinal modulus of elasticity. The aromatic ring, as well as the
conjugation of electrons gives the material high thermal stability, chemical stability and mechanical
stiffness. The hydrogen bonds in the transverse direction and covalent bonds in the fibre axis
direction lead to a great mechanical property anisotropy.

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

Fibre Properties

Aramid fibres are characterized by medium-to-ultrahigh strength, medium-to-low elongation and moderately
high-to-ultra high modulus with the densities for crystalline fibres ranging from 1.35 to 1.45 g/cm 3. Fibres of low
orientation MPD-I (eg Nomex) have a density of 1.35 g/cm3. Fibres from PPD-T (eg Kevlar) have a density of ~
1.45 g/cm3.

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

Chemical Properties

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

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

Aramid fibres are exceedingly difficult to dye by conventional methods due to their very high T g. The aromatic
nature of p-aramid is responsible for a substantial absorption of UV light, which in turn leads to a change of
colour due to oxidative reactions as well as drop in fibre properties.

Thermal Properties

Aramid fibres do not melt in the conventional sense because decomposition occurs simultaneously. Pyrolysis of
poly (p-phenylene terephthalamide) fibre leads to products p-phenylene diamine, aniline, benzonitrile etc.
indicating a homolytic cleavage of amide bond. The differential scanning calorimetry studies of PPD-T reveals
moisture evolution of about 100C, a second order transition at 360 C, followed by melting and chemical
decomposition at 500-575C. Glass transition temperature (Tg) range from 250C to > 400C. Some aramid
fibres such as Nomex, shrink away from a high heat source or from a flame. Aramid fibres characteristically burn
only with difficulty because of high LOI values. Burning produces a thick char that acts as a thermal barrier.

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

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

Mechanical Properties

Typical stress-strain curve of Kevlar aramid yarn as compared to other industrial filament yarns is shown in
Figure. 13. These curves show that Kevlar yarn has a tenacity of 22 gpd, which is more than 5 times that of
steel wire and twice that of nylon, polyester or glass fibre. Kevlar shows an unusually high initial modulus of 475
gpd, which is twice that of steel wire and fibre glass. As a spun fibre Kevlar 29 has a modulus of 62 GPa. Heat
treatment under tension increases crystalline orientation. The resulting fibre, Kevlar 29 has a modulus of 131
GPa. The outstanding high strength of Kevlar can be attributed to:

1. Its aromatic nature and amide group.


2. High crystallinity and orientation.
3. Individual polymer strands of Kevlar are held together by H-bonds that form between the polar amide
groups on adjacent chain. The mechanical properties of Kevlar are also shown in Figure 14.
4. The aromatic components of Kevlar polymers have a radial (spoke-like) orientation, which gives a high
degree of symmetry and regularity to the internal structure of the fibres. This is confirmed by bright
synchroton radiation (XANES image). This crystalline-like regularity is the largest contributing factor in
the strength of Kevlar. Allen et al. have introduced the concept of asymptotic modulus as a measure of
orientation 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
When subjected to axial compression or severe bending it shows nonlinear plastic deformation. The fibre exhibits
a yield point at a compressive strain of 0.3-0.5%. This corresponds to formation of structural defects known as
Kink bands (at 45-60 to the fibre axis). These bands are related to compressive buckling of the aramid
molecules by molecular rotation of the amide C-N bond, which in turn reflects weak lateral properties of these
highly anisotropic materials.

Fatigue behaviour of aramid is also dependent on the mode of fibre deformation (tension vs. compression). With
tension fatigue no failure is observed even at loads as high as 60% of breaking strength and 10 7 cycles. Tensile
failure initiates at the fibril ends and propagates via shear failure between the fibrils. Skin-core gradient in the
fibre causes non-uniform load sharing and hence reduces strength. However, compressive fatigue of organic high
performance fibres is significantly worse. The retention of tensile strength decreases with increased compressive
strain. At 0.5% strain no strength loss is observed even after 106 cycles, while at 1% strain, loss is observed
within 103 cycles.

Poly (p-phenylene terephthalamide) fibre exhibit very low creep even at elevated temperature. At a load of 0.5
of breaking load after 10-5 sec, creep strain for Kevlar is only 0.3%. The longer life time characteristics of high
melting polymer are mainly attributed to high activation energy of primary bond breaking. Kevlar creeps under
high stresses. Creep rate is almost uniform and the amount of creep strain increases linearly with log (time) to
break.

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 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. Its inherent dielectric strength,
mechanical toughness and thermal stability provide high usability and reliability. The para-aramid (KevlarTM)
provides unique combinations of toughness, extra high tenacity and modulus and exceptional thermal stability.
So end use of para-aramid cover a broad range of industrial, aerospace, military and civilian applications, which
include cut, heat and bullet/fragment resistant (ballistic) apparel, hard armours, brake and transmission friction
parts, reinforced tyres and rubber goods, ropes and cables, various forms of composites, filament wound
pressure vessels, industrial gloves, circuit board reinforcements etc., Kevlar 49 HS(High strength) is prepared by
Du Ponts New Fibre Technology in 1997, which is specifically intended for filament winding applications and has
a tensile strength 25% higher than that for standard Kevlar 49, giving it a combination of high strength, low
weight and good impact resistance. This allows filament wound composite cylinders to be used for higher
pressure duties, such as oxygen and industrial gas bottles, fuel tank, rocket motor casings, electrical switch gear
devices and off-shore flexible pipes. Other copolymers containing combination of meta and para substituted
monomers have been developed for optimum properties. While each application has its specific requirements,
almost all of them characteristically utilize high strength, high modulus, high toughness, thermal and
dimensional stability, low creep, and light weight of these fibres. The various applications are shown in Table 2.

Table 2. Applications of Different Aramid Fibres


Copyright IIT Delhi 2009-2011. All rights reserved

MODULE 2. HIGH STRENGTH HIGH MODULUS FIBRES


2.2 Other Rigid Rod Polymers such as PBZT, PBO, PBI (2 Lectures)
Fibres based on Aromatic Heterocyclic Polymers
The fundamental science of structure-property relationship developed in aramids has been further extended to
form heterocyclic rigid rod polymers. In these polymers, the structures are even more rigid than those of p-
aramids and pose greater difficulty in processing.

Classification:

Heterocyclic rigid-rod polymers can be classified into three categories

Polybenzazole
Polybenzimidazole
Polypyridobisimidazole

As shown below in Figure 1, polybenzazole polymers abbreviated as (PBX) include polybenzothiazoles (PBT) and
polybenzoxazoles (PBO). The term also includes some semi rigid polymers such as poly (2,5(6)-benzoxazole)
(ABPBO). The key structural feature of these two polymers is the formation of the benzothiazole and benzoxazole
ring structures.

Figure 1. Structures of PBT & PBO


Polybenzimidazole (PBI) fibre was commercialized for its thermal stability in 1983 by Celanese. More recently,
the poly(2,6-diimidazo(4,5-b:4,5-e) pyridinylene-1,4(2,5-dihydroxy-) phenylene) (PIPD), 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


Manufacture of Polybenzazoles
PBO or cis-PBO is synthesized by condensation polymerization of 4,6-diamino-1,3-
benzenedoldihydrochloride(DABCO) with terephthalic acid (TA) at 60-80 C, while trans-PBT is based on 2,5-
diamino-1,4-benzene-dithioldihydrochloride (DABDT) and TA. Due to the high cost of manufacturing of PBT, PBO
fibres have become more popular. The polymerization is carried out in poly (phosphoric) acid (PPA) solvent and
molecular weights of about 50000-100000 g/mol corresponding to about 200-400 repeat units per chain are
obtained. In synthesis of PBO, PPA plays a role as a solvent as well as catalyst and dehydrating agent. The
spinnable solutions are obtained directly from the polymerization mixtures. Extensive research has been carried
out to understand the PBO polymerization mechanism.

These polymers decompose at high temperatures without melting and are soluble in very few solvent systems
due to their rigid molecular backbone. PBO is soluble in strong protonic acids such as PPA, methane sulfonic acid
(MSA), chlorosulfonic acid, and trifluoroacetic acid via backbone protonation, which weakens intermolecular
interaction and reduces chain stiffness. Several research groups have studied the solution properties of cis-PBO
and have confirmed the high chain rigidity from the exponent value of 1.8 in the MarkHouwink equation in MSA
at 30 C.
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. PBO fibres are prepared using 13-17% solid
content in poly-phosphoric acid solution at 60-90 C. The structure formed during coagulation shows a network
of oriented microfibrils. Heat treatment at 450-500 C for one minute under tension results in about eight times
and 10-20% improvement in modulus and strength, respectively. Similarly after high temperature treatment, the
modulus of PBT fibres exhibits a remarkable improvement of 0.8-16 times while the fibre strength increases
approximately by 50%. Improvement in overall axial orientation, crystal perfection and lateral order lead to
improved mechanical properties. PBO fibres have been commercialized by Toyoba Co. Ltd., Japan under the trade
name Zylon.
The tensile strength and modulus of PBO fibres were reported to be as high as 5.8 and 352 GPa (experimental
fibre), respectively. The mechanical properties of PBO fibre depend on polymer molecular weight, as well as on
processing and post processing conditions.
Tensile strength and modulus retention rates of PBO fibres have also been investigated under various
environmental conditions such as temperature, humidity, and exposure to ultraviolet and visible light. At 400 C,
PBO fibre (Zylon HM) retains 75% of the room temperature modulus. However, high temperature with humidity
has a drastic effect on strength. At 250 C with saturated steam, the strength retention in PBO is below 20% of
its room temperature value. Therefore, PBO fibres should be stored in humid-free environment. PBO tensile
strength also drops sharply with UV exposure in the initial stage, which indicates that the products of PBO fibre
for outdoor use have to be protected from the UV radiation. Exposure to visible light also affects PBO strength.
For example, one month exposure to two 35 W fluorescent lamps placed 150 cm away from the sample is
reported to reduce the PBO fibre tensile strength to nearly 70% of its original value. The excellent chemical
resistance to various organic solvents, acids, and bases leads to high strength retention; however, the PBO
staple fibre showed low resistance under acid and base at high temperature. Besides tensile properties, fibre
dimensional stability is also important for structural materials. The thermal shrinkage of PBO fibre after hot air
treatment for 30 min without applying load was only about 0.2%, while under the same conditions, p-aramid
and co-polyaramid exhibited about 0.5 and 0.7% shrinkage, respectively. Based on the creep testing, at 60% of
the failure stress, failure time of 19 years is predicted for the Zylon HM fibre. Abrasion resistance of PBO on
metal is higher than that of aramid fibres under the same load, while both the PBO and aramid exhibit much
lower abrasion resistance than that of nylon or ultra high molecular weight extended polyethylene.

PBO fibres have specific values of strength and stiffness in excess of all other materials. These fibres also have
excellent thermal properties and find application in heat-resistant felt in glass industry. Owing to these excellent
properties, PBO fibres have vast range of applications. However, these fibres have poor performance under
compression. This has led to interest in increasing the lateral strength in PBO fibre after formation.
Unfortunately, attempts to introduce hydrogen bonds in PBO did not help as the hydrogen bonds were found to
be formed intra-molecularly rather than intermolecularly.

PIPD or M5 Fibre
In order to develop rigid rod polymers with good compressive properties, rigid rod like polymers with the
possibility of forming strong intermolecular hydrogen bonds are desirable. Polymerization of 2,3,5,6-tetra
aminopyridine with 2,5-dihydroxyterephthalic acid (DHTA) can result in a polymer with hydroxyl groups at
appropriate position to contribute to the hydrogen bond network envisioned for improved lateral strength
One can readily observe that that the structure of PIPD or M5 is similar to PBO and PBT except for the following
differences

1. The central aromatic ring in M5 is pyridinyl rather than benzyl


2. Presence of hydroxyl groups at 2-and 5-positions of diacid and
3. The X group in benzazole ring structure is NH.
Polymerization is achieved by the synthesis of the TAP:DHTA 1:1 complex, or TD complex. This complex is
significantly more stable against oxidation than TAP phosphate and it precipitates in a high yield from the
combination of (alkaline) aqueous solutions of TAP and DHTA, Na or K salt upon neutralization. Polymerization by
this route is fast (takes about 4 8 h) and yields high MW polymer with high consistency in relative viscosities.
The polymerization consists of heating the slurry of TD complex in polyphosphoric acid and P2O5 with a trace of
tin powder in a reactor at 130 140 C, under inert conditions. The P2O5 content of the solvent system impacts
the final molecular weight, and obviously only the highest purity TD complex results in formation of highest MW
polymers. At 180 C, the 18 wt% polymer is a nematic and has long relaxation times. Upon cooling it crystallizes
at about 110 C; the crystallized solution melts at about 140 C. The as polymerized solutions with molecular
weight (Mw) 60000-150000 were spun using conventional air-jet wet-spinning at 180 C into a water or dilute
phosphoric acid bath.
The XRD patterns of solidified polymer solution in PPA showed the existence of two different crystal solvate
phases. The crystal solvate phase 1 in the polymer solution at room temperature changed to crystal solvate
phase 2 which starts at 85 C and is completed at 115 C. It disappears above 135 C and a nematic phase
appeared. The transition from nematic phase to the crystal solvate can happen by cooling. The crystallinity of
crystal solvates of PPID is higher than PBO and PBT. The coagulated and washed fibre is isolated as a crystal
hydrate (as spun fibre). This transforms into a bidirectional hydrogen bonded structure during heat treatment
process transforms this into the final high modulus M5 crystal structure. The as-spun fibre shows attractive
mechanical properties, comparable to para-aramid fibres, although the modulus is higher (about 180 GPa). The
as spun fibre excels in flame resistance. The crystal-to-crystal transformation during the hot drawing leads to a
much higher modulus, due to a more slender effective chain and stronger interchain bonding, coupled with an
improvement of the orientation.

The rod like polymer molecules feature internal hydrogen bonds between -O-H groups and imidazole N atoms,
and a network in both directions perpendicular to the rod like chains between imidazole N-H atoms and the O-H
groups. This leads to a high shear modulus and shear strength and thus to good compressive properties of the
M5 fibre. The honeycomb-like structure may be explain the impact and damage tolerance properties of M5
products
The key features of M5 are that it has a higher compressive strength than PBO or PBT, and it is more stable to
UV and hydrolytic action than PBO. It is reasonable to assume that the NH group contributes to the 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
PBO
Property Twaron HM C HS a
M5 experiment c

( toyoba data) b

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) d
0.58 2.1 0.4 1.6
Compr. Strain (%) d
0.5 0.9 0.15 0.5
Density 1.45 1.8 1.56 1.7
Water regain (%) 3.5 0 0.6 2
LOI (%O2) 29 -c 68 >50
Onset of thermal degradation,
450 800 550 530
air
Electr. Conduction - ++ - -
Impact resistance ++ -- ++ ++
Damage tolerance + -- -e ++
Weaving props. + - + +
Knot strength + -- 0 0
The mechanical properties of carbon are evaluated in resin-impregnated strands in order to protect the material
a

against premature brittle failure in the tensile testing machine. The organic fibres are tested as such; filament
averages at a10 cm gauge length are presented
b
Toyobo data
c
Measured in UD composites test bars, three-point bending test, onset of deflection for the organic fibre-
reinforced composites; catastrophic failure for the carbon composites. M5 composites proved to be able to carry
much higher loads than the load at the onset of deflection and to absorb much energy at high strains in a mode
analogous to the flow behaviour in steel being damaged
e
No data

Copyright IIT Delhi 2009-2011. All rights reserved.

MODULE 2. HIGH STRENGTH HIGH MODULUS FIBRES


2.3 Thermotropic aromatic polyesters (1 Lecture)
Wholly aromatic polyesters that form liquid crystalline phase over a certain temperature range in the melt are
called thermotropic liquid crystalline polymers (TLCP) as shown in Figure 1.

Figure 1. Phase change occurs with variation in temperature


To obtain high strength, high modulus fibre, it is required to select polymer having molecular structure in which
polymer chains are packed closely with strong bonds and low elongation. Desirable polymers for this purpose are
aromatic polyesters comprising of highly symmetrical and rigid structure as shown below in Example 1 and 2.

Example 1

Example 2
However, these aromatic homopolyesters have a very high melting point (are infusible) and degrade before
melting.

How to overcome this problem?

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

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

Example

The copolymers of HBA/PET were among one of the first series of TLCP developed into fibres. In these polymers,
the liquid crystalline behaviour appears for compositions exceeding 30% of HBA.

Second, kinks can be designed into chemical structures as shown below.

Example

Third, a disturbance can be made in the lateral packing by introducing large range of pendant groups such as in
the case of p-benzenedicarboxylic acid (TPA)/phenylhydroquinone( PHQ)/(1-phenylethyl)hydroquinone(PEHQ).
Production of Aromatic Polyester Fibres

Commercially available TLCP fibre, Vectran, is produced from the polymer developed by Hoechst Celanese
Corporation in the 1970s. The polymer is obtained by acetylation polymerization of p-hydroxybenzoic acid (HBA)
and 6-hydroxy-2-napthonic acid (HNA) and has a thermal distortion temperature of 180-240 C and a melting
point of 270 C.
Spinning of Aromatic Polyester Fibres

The polymers with intrinsic viscosity in the range of 1.5-3 dL/g can be spun easily from their liquid crystalline
state, in a temperature range of 280 C to 360 C. The spinning process for these thermotropic copolyesters is
similar to the conventional PET melt spinning process. Upon melting, hydrolysis and thermal decomposition of
polymers occur, causing degradation of the polymer. To minimize the decrease in intrinsic viscosity or molecular
weight of the polymer, it is necessary to dry the chips to eliminate moisture in the pellets. Flexible polymers such
as PET generally maintain their viscosity in low shear region, but in case of thermotropic liquid crystal polymers
the viscosity falls linearly as shear rate increases (even in low shear rate region). Some type of lubricant,
normally water, is applied for ease of processing. These fibres attenuate rapidly and solidify within 10 cm from
the orifice without exhibiting any die swell. Also, no subsequent drawing is carried out. Therefore to obtain fine
denier fibre, it is necessary to either use a small diameter orifice or increase spinning draft. The as spun fibres,
which are 10% crystalline, have tenacity of about 10 g/denier, elongation of 0.2% elongation, and initial modulus
of 425 g/denier. On heat treatment below the melting temperature (250-300 C) for several hours, tenacity of
23-28 g/denier is achieved, however the modulus increases only slightly. During heat treatment, the crystallinity
increases to 20% and molecular weight increases by three times. This heat treatment time is much longer
(required for solid state polymerization) than that of a conventional heat treatment process in PET fibres because
in the melt, low molecular weight polymers are usually used in order to ease processing. TLCP fibres are
produced from polymers with varying chemical compositions. Table 1 shows composition of liquid crystal
polymers and fibre properties.

Table 1. Mechanical Properties of Liquid Crystal Fibres

HBA:p-hydroxy benzoic acid, HNA: 6-hydroxy-2-naphthoic acid, PhHQ:phenyl hydroquinone, TA: terephthalic
acid

As shown below, the fibres exhibit very high molecular orientation (compared to conventional polyesters) which
is developed during spinning process owing to the rigid structure of polymer chains.
Figure 2. High molecular orientation of liquid crystal polymer

Several levels of superimposed fibrillar structures similar to p-aramids were observed in the highly oriented
copolyester fibres. Skin-core morphology can also be found in these fibres although it is not as prominent as in
the case of fibres from lyotropic liquid crystalline polymers. The skin core effect is mainly caused by the
acceleration of elongational flow in the surface regions while there is deceleration in the central regions of fibres.
Like aramids, TLCP fibres also show kink band formation with increases flex cycles.However, more energy is
absorbed in kink band formation in TLCP than in aramid, and this results in the significantly increased resistance
to failure in flex folding. The fibres show no creep when loaded <50% of breaking strength. The properties of
TLCP fibres in comparison to other high performance fibres are given in Table 2.

High strength TLCP fibres are used in ropes and cables for dynamic applications, composites, protective
materials, industrial fabrics, medical applications (catheters and surgical device control cables), veterinary
implants and specialty insulating papers (due to excellent dielectric properties and low moisture absorption).

Table 2: Properties of Various Fibres


Copyright IIT Delhi 2009-2011. All rights reserved.
MODULE 2 HIGH STRENGTH HIGH MODULUS FIBRES
2.4 Manufacturing of Carbon Fibres from PAN Precursors, Viscose and
Pitch Fibres (6 Lectures)
Introduction to Carbon Fibres and PAN based Carbon Fibres
The development of carbon fibres has been a distinct achievement in the progress of high performance fibres.
The term carbon fibre refers to materials (filaments, yarns, roving) consisting of at least 92% (mass fraction)
carbon, usually in the non-graphitic state. The attractive attributes of carbon fibres are:

low density,

high specific strength and stiffness,

excellent chemical stability (except in highly oxidizing environments),

biocompatibility

low coefficient of thermal expansion,

excellent fatigue and creep behaviour.

Owing to the amazing structural properties, carbon fibres are used extensively in fibre-reinforced composites for
the replacement of metals in the most critical applications such as:

aerospace

defence

nuclear technology

automobile

marine applications

sports goods

civil construction

biomedical etc.

The use of carbon filaments in electric lamp was first patented by Thomas Alva Edison in 1877. These carbon
filaments had poor mechanical properties and during 1950s there was an added impetus to make stronger
carbon fibres.
As shown in Figure 1, the carbon fibres are composed of large aromatic sheets similar to those in graphite. In
carbon fibre, these aromatic sheets are randomly oriented to each other and such a arrangement is also
described as turbostratic structure while, in graphite the adjacent aromatic sheets overlap with one carbon
atom at the centre of each hexagon (Figure 1(b)).
(a) Irregular stacking (b) regular stacking
Figure 1 Stacking of aromatic sheets in (a) carbon fibres and (b) in graphite
Carbon fibres are produced by controlled oxidation and carbonization of organic precursor fibres. The organic
precursor fibre used for manufacture of carbon fibre, is generally a special textile polymeric fibre
that can be carbonized without melting. The ideal requirements for a precursor are:
it should be easily converted to carbon fibre
gives a high carbon yield and
allows to be processed economically

Among the various precursors, evaluated for manufacturing carbon fibres, only the following three precursors-
are commercially successful.

Viscose rayon
Mesophase pitch, and
Polyacrylonitrile (PAN) fibres

The cross-sectional shape of these precursors are shown in Figure 2.

Figure 2. Cross-sectional shapes of different precursor fibres


Out of these, viscose rayon (carbon yield ~ 30%) is losing its importance in competition to high performance
carbon fibres available from other precursors. Pitch based carbon fibres, however, with high resultant modulus.
General purpose carbon fibres obtained from isotropic pitch have higher yield of ~80% and possess modest level
of strength and modulus.They are most economical and are useful in enhancing modulus and conductivity in
various applications. Mesophase pitch fibres can be heat-treated to enhance to produce very high modulus
carbon fibres.
PAN based carbon fibres are the strongest available carbon fibres. The PAN based precursors are preferred due
to following reasons:
high carbon yield (50-55%)
potential of polymer to undergo cyclization reactions,
lowest fraction of voids (resulting in higher strength and stability) coupled with the flexibility for tailoring
structure of final product

The production process of carbon fibres involves two distinct steps:


Preparation of suitable organic precursor fibre
Conversion of precursor fibre to carbon fibre

The physical properties of carbon fibres vary over a very broad domain owing to the differences in the nature of
the precursor and processing conditions employed for conversion to carbon fibres. The properties of carbon
fibres depend both on the properties of initial polymer and processing conditions used in the carbon fibre
production process. Another important characteristic of carbon fibres is that they can survive very high number
of stress cycles compared to steel as they are not subject to creep and fatigue failure. In carbon fibres, the
conduction of heat occurs by lattice vibrations while the electricity is conducted by diffusion of electrons and
holes.

PAN based Carbon Fibre

The potential for PAN as a precursor was first recognized in Japan in the late 1950s followed by UK and USA in
1960s. Starting with a linear PAN homopolymer containing 68% carbon, a controlled transformation is affected
through a series of heat treatment steps in different environments at progressively increasing temperatures.

PAN based carbon fibres are classified according to the tensile properties and the heat treatment temperature as
follows.
Classification based on Properties
Ultra-high-modulus, type UHM (modulus >450 GPa)
High-modulus, type HM (modulus between 350-450 GPa)
Intermediate-modulus, type IM (modulus between 200-350 GPa)
Low modulus and high-tensile, type HT (modulus < 100 GPa, tensile strength > 3.0 GPa)
Super high-tensile, type SHT (tensile strength > 4.5 GPa)

Classification based on Final Heat Treatment Temperature:

Type-I, high-heat-treatment carbon fibres (HTT), where final heat treatment temperature is above 2000
C and can be associated with high-modulus type fibre.
Type-II, intermediate-heat-treatment carbon fibres (IHT), where final heat treatment temperature is
around or above 1500 C and can be associated with high-strength type fibre.
Type-III, low-heat-treatment carbon fibres, where final heat treatment temperatures not greater than
1000 C. These are low modulus and low strength materials.
Table1. Classification and Properties of PAN based Carbon Fibres a

Carbonization temperature & High High modulus Ultra high modulus


c d

properties strength b

Carbonization temperature ( C) 1200-1400 1800-2500 2800-3000


Carbon % in the fibre 92-96 99 99
Filament diameter (m) 5.5- 8.0 5.4-7.0 8.4
Density g/cm 3
1.75-1.80 1.78-1.81 1.96
Carbon content (%) 92-95 92-99 99
Tensile strength (MPa) 3105-4555 2415-2555 1865
Tensile modulus (GPa) 228-262 359-393 (483-690), 577
Elongation at break (%) 1.3-1.8 0.6-0.7 0.38
a. strand data, b. Thornel T-300,T-600, c. Thornel Y-50,Cellion G-50, d. Celion GY-70

Characteristics of Acrylic Precursors suitable for Carbon Fibre

The structure and properties of carbon fibre are dependent on the initial precursor fibre properties as well as the
conversion process governing the structural changes taking place during the formation of carbon fibre. Hence, in
order to obtain carbon fibres with superior mechanical properties, acrylic precursor fibre should possess high
tenacity and modulus and during the transformations induced by heating of polyacrylonitrile (under optimum
conditions), the initial supermolecular structure of PAN and orientation of chains within each fibril are required to
be improved (or at-least maintained). This means that the spinning process should result in defect free highly
oriented fibres. Additionally the polymer characteristics such as molecular weight, comonomer type and
composition of precursor polymer also have a strong influence on the spinnability of precursor polymer,
properties of precursor fibre and processability of precursor fibre to carbon fibres. The following flow chart
(Figure 3) explains the influence of the precursor polymer and fibre characteristics on the properties of final
carbon fibre properties.

Related Properties of polymers Related Properties of fibres

Figure 3. Effect of polymer properties on carbon fibre properties


PAN precursors used for production of carbon fibres are known as special acrylic fibres (SAF). SAF forming
polymer should possess following properties:
High molecular weight (M w~200000-500000)
An appropriate polydispersity (MWD= 2-3)
Minimum molecular defects
Nature and proportion of comonomers
The precursor fibre should have following properties-
A fine denier (1-2 dtex)/ defect free fibre
Absence of foreign particles/impurities
Less number of filaments per tow
High strength and modulus ( high axial orientation of molecular chains)
A broad exothermic peak due to nitrile group cyclization during stabilization initiating at a lower
temperature.
Should result in high carbon yield (>50 %)

Principles of Production of carbon fibres from PAN precursors


The manufacturing of carbon fibres based on acrylic fibres involves three successive stages of heat treatment:

Figure 4. Steps for conversion of PAN precursor to carbon fibre


Why is the stabilization necessary prior to carbonization?

The thermal stabilization of PAN precursor is the most crucial step in the production of carbon fibres.It converts
the PAN precursor into thermally stable structure capable of withstanding high temperature processing in
subsequent steps. The stabilization of precursor can be accomplished either by heat-treatment in inert or
oxidizing atmosphere. The stabilization in inert atmosphere (curve b in Figure 5) is faster and produces carbon
fibres with poor mechanical properties with low carbon yield( 30-40% at 1000 C).However, stabilization in
air/oxygen atmosphere (curve a in Figure 5) takes longer to complete cyclization reaction and produces
carbon fibres with good mechanical properties and higher carbon yield( ~ 60% at 1000 C). Also, fusion of
oxygen containing groups in the polymer backbone provides greater stability to the ladder polymer to sustain
high temperature carbonization treatment. The precursor is stabilized by controlled heating (180-300 C) in
oxidative environment to form a thermally stable structure capable of withstanding high temperature processing
in subsequent steps at high rates with good yield.
Figure 5. DSC exotherms of PAN in a)air and b) nitrogen.

he stabilization chemistry is complex and in the presence of oxygen is accompanied by chain scission, cross-linking,
ehydrogenation, formation of oxygen containing groups and cyclization take place. The chemical reactions are
esponsible for change in the colour of the precursor fibre to yellow, brown and ultimately black.

Figure 6. Sequence of reactions occurring during stabilization


The cyclized structure is stable towards heat and can be converted to turbostatic carbon on subsequent
carbonization at high temperatures. Since this cyclization reaction is highly exothermic, attempts have been
made to choose PAN precursor and stabilization conditions in such a manner that the heat released during the
stabilization process is dissipated without adversely affecting the properties of ultimate carbon fibre. Therefore,
comonomers containing 0.5 to about 2 mole% acidic comonomers, such as itaconic acid are used (higher
amounts would reduce the carbon yield).These monomer lowers the stabilization temperature. Incorporation of
neutral acrylate monomers slows down the cyclization reaction and reduces the heat release rate. Both these
effects facilitate stabilization reaction. A qualitative curve showing the effect of presence of comonomers is
shown in Figure 7.

The acidic comonomers such as acrylic acid (AA), methacrylic acid(MAA) and itaconic acid(IA) increases the
segmental mobility, modify the fibre morphology, improve the polymer solubility as well as spinnability, lower the
glass transition temperature, increases the hydrophilicity and facilitate and depress the onset point of cyclization
of nitrile groups during thermo-oxidative stabilization of acrylic precursors prior to carbonization. The
comonomer leads to controlled stabilization process paving path for manufacturing of PAN based carbon fibres
with superior properties. The effectiveness of different monomers in reducing the initiation temperature of
cyclization can be expressed in the order itaconic acid>methacrylic acid>acrylic acid>acrylamide. The superiority
of itaconic acid can be attributed to the presence of two carboxylic acid groups, increasing the possibility of
interaction with nitrile group.

Incorporation of neutral acrylate monomers slow down the cyclization reaction and to reduce the heat release
rate. Neutral acrylate monomers also act as stabilizers and aid the spinning process. Both these effects facilitate
stabilization reaction. Figure 7 shows a qualitative showing the effect of presence of comonomers.
Figure 7. Effect of comonomers on structure stabilization
The process of stabilization involves three main phenomena:

mass transfer

heat transfer

shrinkage

Mass transfer occurs due to diffusion of oxygen into the precursor fibres and evolution of volatile products such
as HCN, NH3, and water vapour. Heat transfer takes place due to occurrence of exothermic reaction of
stabilization. The stabilization process therefore is diffusion controlled and rate of diffusion is in fact the rate
determining step of cyclization reaction. For the same reason finer fibres with high surface area are preferred.
Therefore the special acrylic fibre suitable for precursor application is drawn at least 12-16 times. The fibre also
undergoes substantial physical as well as chemical shrinkage. As shown in Figure 8, the physical shrinkage is
attributed to the entropic recovery of a drawn and quenched fibre. The chemical shrinkage occurs mainly due to
the formation of cyclized ladder structure.
Figure 8. Shrinkage of fibre with stabilization time
Effect of process conditions during thermo-oxidative stabilization
The stabilization process is greatly influenced by the tension during thermo-oxidative stabilization, the heat
treatment temperature, the treatment medium, pre-stabilization treatments, and the characteristics of the
precursor.

As this is an exothermic reaction, the manner in which heat dissipation takes place decides the further
performance of the fibre. In order to achieve this, slow heating rate must be used to avoid run-away reactions
occurring during the stabilization process. As shown in Figure 9, excessive heating (higher stabilization
temperature) results in poor properties due to burning out of fibre while insufficient heating (lower stabilization
temperature) leads to incomplete reaction and damage of fibre during carbonization step. Stabilization can be
achieved isothermally by heating at constant temperature, but is time consuming. Alternate more practical
methods are step wise increase in temperature or one-step stabilization, with temperature rising along a tubular
furnace.

Figure 9. Effect of heating rate and final stabilization temperature on properties of carbon fibres
The chemical structural changes occurring during stabilization are discussed in detail in several reviews and
books. This step is the decisive step as it largely governs the final structure of fibre and hence its ultimate
mechanical properties.

Carbonization process
This step involves heat treatment of stabilized PAN fibre in an inert atmosphere under low or very little tension.
Chemically, carbonization is the process of fusion of ladder polymer chains of stabilized fibres and elimination of
all elements other than carbon to form graphite like structure. As shown in Figure 10, the carbonization process
is carried out in two different heating zones. The first heating zone, in which fibres are treated up to 600 C, is
very crucial and involves intermolecular crosslinking of stabilized fibre elimination of water or other gases. This
zone, requires a low heating rate (less than 5 C/min) so as to keep the mass transfer slow. A faster mass
transfer at higher heating rates may cause surface irregularities in the form of pores. Most of the volatiles are
evolved below 1000 C, and only carbon and some nitrogen( ~ 6%) are left. The dehydrogenation, dehydration
reactions occurring in these steps are shown in Figure 11-12.

Figure 10. Schematic representation of carbonization process


Figure 11. Schematic representation of water elimination reactions

Figure 12. Schematic representation of dehydrogenation reactions


In the second zone, in which the fibres are heated between 600-1300 C, higher heating rates can be used
because of the reduced possibility of damage due to exothermic reactions. Inert gases and non-oxidizing media,
such as HCl, BBr , ZnO etc., have been used to avoid oxidative degradation at such high temperatures. Nitrogen
3

and hydrogen cyanide are evolved due to intermolecular crosslinking of polymer chain as shown in Figure 13,
and hydrogen is evolved as a result of dehydrogenation. The carbon atoms of one cyclized sequence fit into the
spaces left by the nitrogen of the adjacent sequence leading to the growth of graphite like structure in the lateral
direction.
Figure 13. Intermolecular Cross-linking of Polymer Chains
Graphitization Process

This step involves heating the carbonized fibre under tension at about 1200- 3000 C in an inert atmosphere.
Nitrogen cannot be used as inert medium because above 2000 C it becomes active and forms cyanogens by
reacting with carbon fibres. This leads to an increase in the size and alignment of graphite crystals resulting in
enhanced mechanical properties.

Structure of PAN based Carbon Fibres


The microstructure of the polyacrylonitrile (PAN) precursors can strongly affect the structure of the carbon fibres
which determine the final mechanical properties of carbon fibres. However, the physical and chemical structural
transformations that take place during heat treatments are extremely complicated. The linear chain structure of
PAN based precursor is transformed to a planer structure.

Carbon fibres have a sheath core type macroscopic structure, with greater perfection and of packing and
orientation of graphite layers and larger crystallites than that in the core. The difference in the fibre density
(~1.8 g/cm3) and the crystal density (~2.1 g/cm3) of carbon fibres suggests the presence of an appreciable
porosity (~16-18%) due to presence of sharp-edged, needle-like pores/voids in the fibre direction.

Carbon fibres consist of polyaromatic carbons and exist as turbostatic carbon,shown in Figure 14. The crystal
structure of turbostatic carbon with a distance of 0.34 nm between the layers of planes is greater than that in
the graphite. Wide angle X-ray diffraction has been used to obtain the characteristic parameters for carbon
fibres.

Figure 14. Crystal Structure of Turbostatic Carbon


These graphitic layers form the basic structural units in the shape of ribbons of 6 nm average width and a length
of several hundred nanometers. About 10 to 14 such ribbons pack in bundles to form fibrils observed in electron
micrographs of carbon fibre. In the electron microscope the fibrils in carbon fibre are observed parallel to the
fibre axis and the ribbons pass from one fibril to the neighbouring fibril, producing elongated gaps between the
fibrils (Figure 15). During heat treatment at high temperature during graphitization, such defects in the
turbostatic graphite layer migrate to form a longer stretch of perfect order and needle- like voids between
graphitic crystals.
Figure 15. Schematic showing structure of Carbon Fibre
The structure of carbon fibre ribbon is believed to be a columnar arrangement of disoriented graphite crystallites
parallel to the ribbon length. The idealized tetragonal crystallites are stacked above one another, with slight
disorientation between the crystals in the direction of fibre axis, trapping sharp needle-like voids, where the
boundaries between the stacks represent the disordered regions.

In a more recent description of carbon fibre structure representing differences in sheath and core is shown in
Figure 16. The sheath region appears to be more ordered and lamellar while in the core, extensive folding can
occur. The model also demonstrates the interlinked crystallinity of HM carbon fibre showing tilt, twist boundaries,
porosity and overlapping boundaries.

Figure 16. Model explaining structure of high strength PAN-based carbon fibre
Carbon Fibres from Cellulosic Precursors
Cellulose is the second important raw material for large- scale production of carbon fibres because it degrades
without melting. Cellulosic precursor fibres, although of considerable historic significance, are no longer an
important source of carbon fibres. To make continuous carbon fibres continuous viscose fibre precursor is
required, which immediately imposes a limitation, since majority of current viscose production is chopped to
form a staple product. Secondly, specific end-users superimpose their own stringent specifications, like presence
of certain trace elements etc. The most common end uses for these carbon fibres are ablative shields and high
temperature packing materials.

Contrary to PAN and pitch precursors, limited information is available on production of carbon fibres from
cellulosic precursors.

Production of Carbon Fibres from Rayon

Different stages of production of carbon fibre from rayon precursor are shown schematically in Figure 17.
Figure 17. Schematic diagram showing production of cellulose based carbon fibres
The repeat unit of cellulose in rayon contains hydrogen and oxygen, which can result in the
elimination of five molecules of water resulting in a theoretical weight loss of 55.5%.The actual
weight loss is about 70-90%.This excessive weight loss is attributed to chain-splitting reactions
involving CO2, CO, alcohols, ketones, and a number of other carbon containing compounds.
This process occurs through several stages. In the first stage, between 25-150 C, there is physical desorption of
about 12% absorbed water with a small degree of change in lateral order. This is followed by an intramolecular
dehydration from the H and OH fragments present in the cellulosic unit between 150-240 C. Finally, thermal
cleavage of the glycosidic linkage and scission of ether bonds and some C-C bonds via free radical reaction (240-
400 C) occurs. This leads to the formation of large amount of tar, water, CO and CO . (Figure 18)
2
Figure 18. Sequence chemical reactions occurring during conversion of viscose precursor to
carbon fibre
In addition, when a glycosidic linkage is split, it forms a levoglucosan (1, 6-anhydro--D-glucopyranose). On
pyrolysis, this levoglucosan unit breaks down to give flammable products and this reduces the ultimate yield of
carbon fibre. Therefore, the formation of levoglucosan is not desirable. The dehydration reaction (stage 2) and
the thermal scission (stage 3) are competitive reactions. Since the removal of CH OH groups starts at 120 C,
2

the early removal of these groups can prevent the subsequent reaction leading to formation of levoglucosan at
250 C. Hence, holding the temperature in initial stages below 250 C is an effective way of improving the
carbon yield.

At 400 C and above, further thermal cleavages result in the formation of carboneous intermediates and four
carbon residues. Between 400 and 700C, these structures polymerize through condensation reactions involving
removal of H above 400 C into a carbon polymer with graphite like structure. Interestingly, the longitudinal
striations present on the surface of the original cellulose remain on the surface of carbon fibre, in spite of
occurrence of variety of chemical transformations.
Figure19. structure of a) four carbon residue and b) fused structure
Carbonization at higher temperatures ranging between 1000 and 1500 C in inert atmosphere further improves
the mechanical properties. A marked reduction in the resistivity is observed during heat treatment between 500
and 1000 C. This has been attributed to the formation of aromatic ring structure.
Further graphitization of these fibres, under strain at 700-2700 C, causes longitudinal orientation of
the planes resulting in high modulus carbon fibre. The four carbon residues align themselves with
long dimension parallel to the b axis, joining together to form a chain polymer along the original
cellulose direction. The adjacent chains then condense to form six-carbon graphitic structures as
illustrated in Figure 20. According to this scheme, the cellulose b axis, which is 10.3 long shrinks to
twice the length of the graphitic b axis (8.25 ). The youngs modulus of resulting graphitized fibre is
directly related to the graphitization temperature and the amount of stretch applied.

Figure 20. Transformation of cellulose to graphite like structure


Carbon Fibres from Pitch Precursors
Preparation of Pitch Precursor

Pitch can be defined as thick, dark coloured bituminous substances obtained as a result of industrial destructive
distillation processes, obtained as deposits on the earth surface, or manufactured from a specially selected
feedstock. The properties of carbon fibres depend on the tropicity of pitch used for producing precursor fibres.
Figure 21. Steps showing conversion of pitch to carbon fibres
The carbon fibres made from isotropic pitch have low strength and are also referred to as general purpose
carbon fibres or isotropic carbon fibres. The isotropic pitches are prepared from high-boiling fractions of
petroleum feedstocks, usually heavy slurry oils produced in catalytic cracking of crude oil. A typical commercial
pitch is Ashland Aerocarb 70, which has a softening temperature of 208 C and a viscosity of 1Pa.s at 278 C.
Pitches may be subjected to additional treatments to reduce low molecular weight components selectively.

High-performance fibres are made from Mesophase Pitch, which is a discotic liquid crystalline material,
containing highly oriented molecules termed as mesophase.

Mesophase pitch preparation has three main steps:


Highly aromatic feedstock,
Process for polymerising the molecules,
Process for separating out the unreacted feed molecules
When polymerised the pitch molecule will have characteristics similar to the molecule shown in Figure 22

Figure 22: Structure of typical pitch molecule


A typical process for making mesophase pitch preparation is shown in the Figure 23
Figure 23. Process for Mesophase Pitch Preparation
Mesophase pitch consists of molecules of two or three aromatic molecules that are stacked face to face in slight
overlapping pattern and are also known as basic structural units (BSUs).

High-performance carbon fibres are typically melt spun, and spinning technology is the same for all pitch types.

Figure 24. Influence of spinneret design on fibre morphology


The aromatic structure of molecules in mesophase pitch results in formation of optically ordered liquid crystals
which are either liquid or solid depending on temperature. This affects the rheology and performance during
processing. This necessitates the proper understanding of rheological behaviour of the pitch to produce uniform
filaments by melt spinning.

Various types of fibre structures have been produced depending on the spinneret design. The typical fibre
structures shown in Figure 24, are named as as pacman radial (a), wavy radial (b) and severe pacman (c).
The fibres with pacman cross-sections are known to have longitudinal splits which may adversely affect
physical properties. In the downstream processing steps, no significant change in the structure is observed.
However, the heat treatment helps in densification of the initial structure, i.e. increases the packing to increase
tensile and thermal properties and modulus.

The use of non-round pitch carbon fibre cross-section can help in enhancement of fibre adhesion to matrices or
improved surface characteristics.

Conversion of Pitch Precursor to Carbon Fibres

The pitch precursor fibres, as spun are very weak and thermoplastic in nature. These need to be chemically
treated to render them suitable for subsequent carbonization. This process is called stabilization or
thermosetting.

Stabilization: This is accomplished by oxidation treatment in air, O or an O /N mixture. Several other


2 2 2

alternative treatments using NO, SO or HNO are also known. The control of the oxidation process is critical,
2 3

since underoxidized fibres will remain partly thermoplastic and may result in undesirable fusion of filaments in
subsequent carbonization at higher temperatures. This will produce carbon fibre with poor tensile strength. On
the other hand, over-oxidation will produce brittle product and will reduce the graphitizability of pitch.

An isotropic pitch has lower degree of condensation, higher hydrogen content, and a lower softening point.
Therefore, isotropic pitch precursors generally require about 3 h of treatment in a 20% oxygen atmosphere to
form an oxygen bridge structure.

Adequate stabilization of a typical mesophase precursor fibre can generally be achieved in ~40-150 min by
treatment at 260 C. The time required for stabilization depends on the chosen oxidizing atmosphere,
temperature, the diameter of precursor fibres, the type of pitch precursor, its mesophase content and molecular
weight distribution. The average mechanical properties of mesophase fibres before and after stabilization are
given in Table 2.
Table 2 : Properties of pitch based carbon fibres

Carbonization :

Carbonization process is required to remove hetero-atoms like H, N, O and S in the form of H O, CO , CO, N , SO ,
2 2 2 2

CH , H and tars. The highest weight loss is observed to occur in the initial stages of carbonization. Therefore, an
4 2

initial low temperature carbonization at 700 C for 30 s to 5 min is carried out to avoid disruption of fibre
structure. The sequence of structural changes occurring during various carbonization stages are shown in Figure
25.
Figure 25. Mesopitch and High Modulus Carbon Fibres from Pitch
The tensile strength and modulus of carbon fibre made from mesophase pitch increase with increase in
treatment temperature. This is attributed to increasing degree of perfection in the structure. With an isotropic
pitch based fibre the strength and modulus change only slightly.
Graphitization
The mesophase pitch based fibres on further heat treatment under highly controlled atmosphere produces fibres
with a high degree of orientation, where carbon crystallites are parallel to fibre axis. The structural changes
occurring at different heat treatment stages are shown in figure below.
Petroleum-based Pitches
Coal-tar based Pitche

Figure 26. Stages of graphitization of pitch- based fibre


On basis of tropicity two types of pitches can be classified; Isotropic and Mesophase pitch. The carbon fibres
made from isotropic pitch have low strength and are also referred to as general purpose carbon fibres and
isotropic carbon fibres. The isotropic pitches are prepared from high-boiling fractions of petroleum feedstocks,
usually heavy slurry oils produced in catalytic cracking of crude oil. A typical commercial pitch is Ashland
Aerocarb 70, which has a softening temperature of 208 C and a viscosity of 1Pa.s at 278C. Pitches may be
subjected to additional treatments to reduce low molecular weight components selectively.

General purpose fibres are prepared by two different spinning methods:

Centrifugal Spinning
Melt Blowing

In Centrifugal Spinning, molten pitch is forced through small holes in a rotating bowl. The pitch stream is
attenuated into a fibre by centrifugal forces, and is directed against a cutter by a stream of air.The spun fibres
may be cut into shorter lengths by a judiciously positioned knife. The fibres are then processed in the form of a
tow or a mat.
Melt Blowing process gives production rates (per spinneret hole) of the order of 10 times conventional melt
spinning. In this process, a molten stream of pitch is extruded into a high velocity stream of forwarding gas,
which rapidly attenuates the fibre. A commercial die is illustrated. The physics and mechanics of the process are
well articulated.

Copyright IIT Delhi 2009-2011. All rights

MODULE 2. HIGH STRENGTH HIGH MODULUS FIBRES


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


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

Concept of Gel Spinning

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

----------------------(1)
This means that for a particular polymer the critical concentration decreases with increase in molecular weight.
At this low concentration (C*), theoretical maximum drawing is possible. On the other hand if we consider the
drawing of a single molecule from its random coiled state the maximum attainable draw ratio can be predicted
from the following relation:

-------------------(2)
where c is a material constant.

This means that the maximum attainable draw ratio increases with the molecular weight (M) of the polymer. If
the drawing of UHMWPE gel-like fibre is performed under such ideal concentration condition, the above argument
will hold good. However, for economic reasons, the actual spinning is performed at concentrations much higher
than ideal concentration C*.This region is called semi-dilute region.

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

-------(3)
Contrary to equation 2 (applicable for ideal conditions), the maximum draw ratio decreases with increase of the
molecular weight and concentration (for true spinning conditions). This can be explained by an increase of
entanglement number. Therefore, as low a concentration as possible is preferable for higher drawability (C~C*).
Theoretical and experimental C* values for ultra-high strength polyethylene having molecular weights above
1000000 g/mol have been reported to be 0.5-0.7 wt%..

In the above argument, it is assumed that the entanglement points of semi-dilute or concentrated solutions act
as permanent cross-link points even after being solidified (which is not true).For a lower molecular weight
polymer like conventional polyethylene, the higher number of chain ends can easily pass each other through the
entanglement point to produce a high level of so-called disentanglement during the drawing process, which
makes the orientation of lower molecular weight polymers very difficult, because disentangled chain ends are
likely to relax to the random coil state. Even with UHMWPE, the disentanglement possibly occurs during the
spinning process due to crystallization, which reduces the entanglement number to some extent. Therefore, it
becomes necessary to use spinning concentrations higher than critical concentration. This mechanism allows
production of UHSPE even at much higher concentration (C > C*).

Gel Spinning Process for Polyethylene


Polyethylene was the first polymer for which gel spinning was successfully used to produce high performance
fibres. The main reasons for this are:
the highest values of theoretical tenacity and modules 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
The main 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
Ultrahigh molecular weight polyethylene with an average molecular weight one million or more is used. Both the
average molecular weight and the molecular weight distribution are important. From the economic point of view
the concentration of the solution should be as high as possible. Optimum concentrations little above the critical
concentration are used for obtaining high drawabilty. The solvents should exhibit good solubility of PE at high
temperatures (>100 C) but at lower temperatures (<80 C), it should allow easy crystallization of the polymer
chains. After spinning, the solution is cooled in the quench, the solvent is removed and a gel fibre is formed. This
can be done by evaporation or by extraction of the solvent. Various solvents, such as tetralin, decalin,
naphthalene, mineral oil, paraffin oil and paraffin wax, have been reported for gel spinning of UHMWPE.
A relatively high-concentration polyethylene solution is prepared as uniformly as possible, because any
inhomogeneity is expected to cause a defect in the final fibre structure and this will reduce the final mechanical
properties of the fibres. In a typical process shown in Figure 4, a screw-type extruder is used for this purpose.
Figure 4: Spinning of UHMWPE fibre
Spinning Process

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

Figure 5: Influence of spinning speed on extrudate behaviour


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

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

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

Figure 6: Internal Morphology of solutions


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

Figure 7: Drawing Process


After the removal of the solvent, the fibres consist of microcrystalline crystals embedded in non-crystalline
material. In the subsequent drawing stage, the apparently random crystals and most of the non-crystalline
material is transformed into a highly crystalline, highly oriented fibre.

In a commercially feasible process, it is required that the drawing is carried out at high speeds with minimum
fibre breakage. This means that the maximum draw ratio should be proportional to the deformation rate, which
in turn is related to relaxation time of polymeric chains. This requirement is fulfilled, if the following relationship
for the molecular deformation holds good.

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

The value of relaxation time, is affected by the molecular structure of the as-spun fibre structure, i. e. chain
entanglement. Therefore relaxation time is also dependent on both the molecular weight and the concentration
by following expression.

and from equation 1

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

Figure 8: Conversion from lamellae to fibrils


High deformation rates in the spinline result in shish-kebab structure in as-spun fibres rather than lamellar
structure (due to local inhomogenity).

Figure 9: Shish-Kebab Structure


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

During the drawing process, transformation from the shish-kebab structure into the microfibril structure has also
been observed as shown in the schematic diagram in Figure 10 : Model (a) represents the typical shish-kebab
structure mainly observed in as spun fibre, model (c) represents the microfibril structure observed in the fibre
drawn at a high-draw ratio, and model (b) represents intermediate state between state (a) and state (c) often
observed for the drawn fibres.
Figure 10. Fibre Morphology at different Draw-ratios
These fibres are commercially available under the trade name of Dyneema and Spectra. The gel-spun fibres are
characterized by a high degree of chain extension, parallel orientation greater than 95% and a high level of
crystallinity (up to 85%). This gives the fibres their unique properties.

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

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

Table1. Properties of Commercially available HPPE filament yarns

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

HPPE fibres possess a unique combination of performance properties. These fibres have high tenacity and high
modulus like other high performance fibres but are flexible and have a long flex life comparable with general
purpose polyamide and polyesters used in ropes. Dyneema and Spectra fibres have a high modulus but still are
flexible and have a long flex life.
Figure 11. Comparison of Abrasion and Flex Life of Various Fibres
For use in marine environment, HPPE fibre is an ideal material. Because of its low density ( lower than water), it
floats on water and is unaffected by water, sea water or UV light.

Figure 12 Wet knot strength of different fibres


Ropes:

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

Nonwovens constructed by unidirectional layers of HPPE yarns bonded by various thermoplastic matrices (as
shown in Figure 13) are used in ballistic protection against bullets as this gives a far better protection at the
same weight than fabrics.
Figure 13 Construction of Dyneema and Spectra Shield

Copyright IIT Delhi 2009-2011. All rights reserved.


MODULE 3. RESISTANT FIBRES
3.1 Thermally Resistant Fibres (2 Lectures)

As discussed in Chapter 1, besides high mechanical properties, high resistance to temperature and chemicals
are other desirable properties required for certain applications. These materials are also classified as high
performance materials. Unlike the fibres discussed in last module, these materials may not have very high
mechanical properties. Resistant fibres find market in clothing, furnishing and other applications where
resistance to heat or chemicals is necessary for their application.

Resistant fibres can be classified into two broad categories depending upon the nature of resistance offered by
them.
1. Thermally Resistant Fibres- Thermally resistant polymeric fibres are those that resist the thermal
degradation, for acceptable periods during their service lives. Due to their inert structure they may also
be flame resistant.
2. Chemically Resistant Fibres - Fibres which are resistant to chemical attack for acceptable periods
during their service lives at both ambient and elevated temperatures. Generally, these fibres are inert in
nature and may also exhibit flame resistant properties.

Some of the high performance fibres such as the aramids, arimids and others also have good resistance to heat
and certain chemicals.

Thermally Resistant Fibres


These polymers/materials derive their thermal resistance from their aromatic or ladder-like chain structures,
which offer a very high melting (> 350 C) or absence of melting transitions. This class of fibres have overlap
with some of the high modulus-high tenacity materials. Thermally resistant fibres are required for applications
where the textile has to withstand high temperature. In these applications, high strength is not a primary
requirement and in certain cases lower stiffness may be preferred to impart good textile properties in clothing
and upholstery. The thermally resistant fibres are often differentiated only by the severity of thermal
environments and their respective resistance to it or in other words the degree of protection and/durability
demanded in particular end application. These fibres often offer service temperatures well above 400 C, and
higher if shorter times of heat exposure are evident.

Protective clothing, for example, may be required to give protection to flame temperatures (> 1000 C) for a few
minutes while hot-gas filtration fabrics may require continual service exposure temperatures of 120-150 C or so
and be expected to sustain these for days, weeks and even months.

Limiting Oxygen Index (LOI), is used to measure flame resistance of a material. It is the amount of oxygen
needed in the atmosphere to support combustion. Fibres with LOI > 25 are said to be the flame resistant, that is
there must be 25% oxygen present in order to burn them. No one fibre has all the necessary properties for
every fire-resistant application and, the best treatment is to blend them with other fibres to enhance colour and
abrasion resistance, handling and wear characteristics.
In this course we will be learning about inherently flame resistant fibres.

Based on the chemical structure, the inherently thermal resistant fibres can be classified in following main
categories:

1. Thermosets
2. Aromatic polyamides and polyarimids: Aramid, arimid,aramid-arimid
3. Oxidized acrylics or PANOX
4. Polybenzimidazoles: PBI
5. Polybenzoxazoles: PBO

Thermosets

Rapidly crosslinking polymers like the melamine-formaldehydes or relatively unreactive polymers like heat-cured
novolac phenol-formaldehydes can be used to make fibres that have acceptable textile properties. On heating,
these fibres continue to crosslink and eventually char and this gives rise to high levels of fire resistance.

Melamine- Formaldehyde Fibre

Commercially produced melamine formaldehyde fibre is called Basofil .This fibre is produced by condensation
of melamine with formaldehyde, which forms a three-dimensional network characteristic of thermosets. Due to
the crosslinked structure, melamine formaldehyde fibres possess high temperature, flame and chemical
resistance. The condensation reactions for formation of Basofil are:

Figure 2. Chemistry of Condensation Reaction

Generally, on reaction with formaldehyde each primary group of melamine is converted to methyloyl group
resulting in pre-condensates. As the reaction progresses, the reaction mixture turns into a clear solution whose
viscosity increases with temperature and reaction time. Melamine formaldehyde condensation resin in the
viscosity range of 300-3000P is spun into filament form and subsequently cured to form the basofil fibre. The
curing operation is performed at a temperature of 170-320 C. The pre-condensates that are initially formed
continue to condense on heating to result in an insoluble and infusible 3-dimensional polymer which is
characterized as the melamine-formaldehyde resin which forms the basofil fibre. The ratio of methylene (-CH 2-)
to dimethylene ether (-CH2-O-CH2-) bridges depends on the pH and temperature.

The resulting fibre formed with the pure melamine formaldehyde would be too brittle, so to improve the
mechanical properties, modified melamine derivatives are added to reduce the degree of crosslinking.

Properties

Physical properties of Basofil fibres are detailed in the Table 1. These fibres have low thermal conductivity and
excellent heat dimensional stability because of the very high degree of crosslinking. Therefore, on exposure to
flame, these fibres do not melt or drip. They also exhibit excellent chemical resistance with regard to organic and
aromatic solvents and to bases.

Table 1. Physical Properties of Basofil Fibres


Density g/cm 3
1.4
Strength (cN/dtex) 2-4
Elongation at break (%) 15-20
Moisture regain at 20 C & 65% rh (%) 5
Limiting Oxygen Index (%) 32
Continuous Use Temperature (C) 190

End-uses: Typical end-uses are in applications where heat and flame resistance properties and chemical
resistance are required. For example:

High-temperature filtration: In this basofil is used as nonwoven felt based on intimate blend of basofil
with meta-aramid fibres.
Fire blocking and heat insulating felts: In blends with other technical fibres, Basofil enhances the fire
blocking and heat insulating performance of needled fleeces used for protective clothings.
Heat and flame protective apparel: Basofil is used in blends with meta- and para- aramids,FR viscose or
with cotton for making protective clothings for industrial wear,fire fighting apparel etc.

Phenol-Formaldehyde Fibre : Novolac


The phenolic novolac precursor resin is prepared by the reaction of phenol with formaldehyde in the presence of
an acid catalyst. The novolac precursor resin with a relatively narrow molecular weight distribution (average
molecular weight (Mn) of 2000) is used. This precursor resin is melt spun in a solution of formaldehyde and
hydrochloric acid in a bath. The as-spun novalac resin reacts with formaldehyde to form crosslinked network of
methylene and dimethylene ether bonds.
Figure 3. Melamine formaldehyde condensation reaction
The cured fibres are golden in colour. The chemical structure of these fibres contains only carbon, oxygen and
hydrogen. Therefore, when exposed to flame, the products of combustion are principally water vapour, carbon
dioxide and carbon char. There is no emission of HCN, HCl, bromine- and phosphorus containing compounds and
other toxic products of combustion typical of many other inherently flame-resistant and FR-treated organic
fibres. Moreover, since the fibre chars without melting and produces few volatiles, smoke emission is also
minimal and is less than that of virtually any other organic fibre.
The important properties of phenolic resins and fibres are
Low thermal conductivity and hence excellent thermal and electrical insulation
Low specific gravity
Retention of properties at low (even cryogenic) temperatures
Excellent resistance to acids, alkalies, solvents, fuels & steam
High compatibility with resins, elastomers, adhesives and
An excellent precursor for carbon and activated carbon fibres/ textiles

The typical properties of Kynol fibres are listed in Table 2

Table 2. Physical Properties of Kynol Fibres


Colour Golden
Specific gravity (g/cm )
3
1.27
Tensile strength (cN/tex) 12-16
Elongation (%) 30-50
Modulus (cN/tex) 260-350
Loop strength (cN/tex) 19-27
Knot strength (cN/tex) 10-13
Elastic recovery (%) 92-96
Moisture regain at 20 C & 65% rh (%) 6
Limiting Oxygen Index (%) 30-34

Applications
Flame resistant safety products & smoke barriers :

Low specific gravity, virtually no emission of toxic gases in flame (no HCN, etc.), extremely low smoke
generation and high flame resistance of Kynol felts and fabrics have made roads into flame and smoke barriers
and insulation in aeroplanes and other areas.

Resistance to extremely low temperature and heat insulation:

Kynol materials are excellent thermal insulators due to their low thermal conductivity and retention of their
textile properties at extremely low temperatures, even after immersion in liquid nitrogen. These are used in
flexible insulation for liquid natural gas piping, as well as in military sleeping bags - two examples in which
protection against both flame and cold extremes are required.

Other thermally resistant Fibres:

The chemistry and process of other thermally resistant fibres based on aromatic structures and oxidized acrylics
have already been discussed in module 2, under high modulus high strength fibres. In this module only the
specific thermal properties will be discussed.

Aromatic polyamides and polyarimids: These polymers have aromatic groups linked by amide or imide
groups. Their resistance to heat is dependent on the reactivity of C-N bond. In polyarimids, this C-N bond is
strengthened due to the presence of increased conjugation. Therefore, polyarimids have higher thermal
resistance compared to aramids. One example of this class is P84 fibre. This has a LOI of 36-38%.

P 84 Chemical Structure

Oxidized acrylics or PANOX: As the name indicates, these are manufactured by controlled oxidation of acrylic
precursor fibre. These fibres are black in colour and have very high thermal resistance and inherent flame
resistance (LOI -55%), because of their partially carbonized ladder structure.

Oxidized Acrylics or PANOX Structure

Polybenzimidazoles: PBI

The thermal shrinkage of PBI fibres in flame can be reduced by 10% on treatment with sulphuric acid.
Polybenzoxazoles: PBO( Zylon fibres)

PBO is the most thermally stable and flame resistant of all organic polymer fibres commercially available.

These polymers are characterized by:

Rigid and linearly symmetrical repeating aromatic structure


Very high thermal stability and excellent flame resistance, because of the absence of aliphatic CH groups
LOI- 68%

Table 3. Comparative data for thermal resistance of all heat resistant fibres:
Second Maximum
Melting Onset of
order continuous use LOI
Fibre Genus temperature decomposition
transition temperature (%)
(C) (C)
(C) (C)
Melamine
NA NA 370 190 32
formaldehyde
150/air;
Novoloid NA NA > 150 30-34
250/inert
375-430
m-Aramid 275 425 150-200 28-31
(decomp)
p-Aramid 340 560 (decomp) > 590 180-300 29-31
Aramid (P84) 315 - 450 260 36-38
Aramid-arimid < 315 - 380 NA 32
Semicarbon NA NA NA ~200/air 55
450/air;
PBI > 400 NA ~300(est) > 41
1000/inert
PBO - - 650; > 700 inert 200-250(est) 68

Notes: NA = not applicable; (decomp) = with decomposition; (est) = value estimated from literature.

Copyright IIT Delhi 2009-2011. All rights reserved.


MODULE 3. RESISTANT FIBRES
3.2. Chemically Resistant Fibres (2 Lectures)
Chemically Resistant Fibres are used in environments where resistance to hostile chemical environment is
required. Chemical inertness is the key requirement of these fibres.

This is obtained by one or more of following characteristics:

o Strong chemical bonds


o Symmetrical structure
o Absence of reactive side groups
o Backbone free of hydrolysable groups
Polyethylene and polypropylene have acceptable resistance to many chemicals at ambient temperatures,
however they have limited resistance to temperatures above 50 C, especially if oxidising agents are present.
Furthermore, the polymer backbone should be free of hydrolysable functional groups such ester and amide.
Therefore fibres based on aliphatic polyamide and polyester structures; do not show sufficient chemical stability.
Aromatic analogues, however, show greater resistance and so are considered a part of this group as well as of
high-temperature resistant group. A hostile chemical environment may also be at high temperature, therefore a
combination of chemical and thermal resistance is desired. Thus, the fibres discussed within this module do not
have a simple commonality of polymer backbone structure or a common set of chemical properties.

These polymers are based on chemically stable structures formed by:

Halogenated polymers
Polymers containing aromatic structures

The main applications of chemically resistant fibres are in

Wet and dry filtration


Geotextile and geomembrane sectors
Protective clothing requiring specific chemical resistance

These are also used in certain applications where chemical resistance at high temperature is a requirement such
as:

Hot gas and liquid filtration fabrics


Braiding materials in chemical plants
Gaskets
Protective textiles
Conveyer belts
High performance sewing threads
Halogenated Polymers

Chlorinated Fibres: PVDC (ARH)

The chemical structure of the polymeric repeat unit in poly (vinylidene choride) creates a polymer with a high
degree of chemical resistance and a high degree of order. However, the greater degree of order also limits its
processibility in commercially useful forms. Therefore, copolymers with other vinyl and acrylic comonomers, such
as vinyl chloride, acrylonitrile and methyl acrylate (usually present at <15% w/w), are utilised. Dow Chemical
Company developed the Saran fibre based on a copolymer of vinylidene chloride and vinyl chloride. The polymer
melts over the range 160170 C and is melt spun at about 180 C by conventional melt-spinning methods to
yield both multi- and monofilaments. It softens over the range 115160 C, depending upon its copolymeric
character and this limits its service temperature limit. The inherently golden-yellow coloured fibres have
acceptably high tenacities, up to 0.25 N/tex, with breaking strains of 1530%.The moderately low modulus (0.9
N/tex) ensures that even the coarsest filaments have a high level of flexibility. With a moisture regain of less
than 1%, tensile properties are maintained under wet conditions and permeation by chemicals is low. Resistance
to chemicals such as salts, acids, most alkalis, aliphatic hydrocarbons and alcohols is excellent at temperatures
up to 100C. However, resistance to aromatic and halogenated hydrocarbons, ketones, ethers and esters is less,
with temperature playing an important part. Coupled with its chemical resistance is an inherently low
flammability and a limiting oxygen index value of 60%. When in a fire, however, it gives off hydrogen chloride,
which is both toxic and corrosive. Apart from some discoloration, PVDC fibres have excellent sunlight and
weather resistance. Main end-uses are those which demand a high level of chemical, and sometimes soil
resistance and so car-seat covers, outside furniture, public vehicle upholstery and wet filtration are typical.

Fluorinated Fibres: PTFE, PVF, PVDF and FEP (ARH)

The fluoropolymeric fibres are generally very expensive, but due to their extreme chemical inertness and thermal
resistance these are required. Among all fluoro polymers, poly (tetrafluoroethylene) or PTFE is the most notable
generic example.

Resistance to the combined effects of temperature and chemical action is a combination of the inherent stability
and inert nature of the polymer chain, coupled with the efficiency of intermolecular forces and chain order.

Due to high melting point and insolubility, the DuPont Teflon (PTFE) fibres are produced by the extrusion of
fibrillar polymeric suspensions in a viscose (cellulose) dope followed by high temperature sintering to generate a
coherent fibre. This results in brown fibres because of the charred cellulose remnants present. Paste extrusion
process is another technique for processing these polymers. In the paste-extrusion process, PTFE powder is
mixed with a lubricant and preformed into a cylinder, which, are later transformed into film or rod forms. The
calendered film is slit, sintered and stretched to give high-tenacity fibres. This technology enables additives to be
incorporated, such as graphite to improve internal lubrication properties in applications such as packings. The
low density and open structure are ideal for medical applications including dental floss, as well as yielding lower
thermal expansion coefficients ideal for high temperature gland packings. The physical properties and resistance
to selected chemicals is listed in Table 1.

Their chemical resistance is similar to that of Teflon-FEP and superior to PVDC, PVF and PVDF. These latter will
degrade in 98% sulphuric acid, 70% nitric acid and 50% caustic soda solutions at elevated temperature,
whereas ECTFE is resistant. The selected examples of chemical resistance listed in Table 2 shows behaviour
considerably inferior to that expected of PTFE fibres but still superior to other chemically resistant fibres,
including others within the fluorinated group. Thus, both ETFE and ECTFE fibre types are ideal for use in filter
screens and cloths, column packings, braided sleevings, gaskets and conveyor beltings, for example, where
extreme chemical resistance at temperatures as high as 150 C is required.

Table 1. Physical Properties of Selected Chemically Resistant Polymers

Tenacity
Genus Breaking strain(%) Tm (C) Tg (C) Max usage temp (C) LOI (%)
(N/tex)
PVDC 0.20 15-30 171 - 115 60
PTFE 0.14 20 347 177 290 98
PVF 0.19-0.39 15-30 170 100 150 --
PVDF 0.43 25 156 100 149 44
FEP 0.3 25 241 149 180 48

Chemically Resistant Fibres based on aromatic ring containing polymers

Aromatic ring containing polymers:


The presence of aromatic groups within the polymeric chains bonded together by relatively inert groups is
another category resulting in good chemical resistance. Since, the melting of these polymers occurs prior to their
decomposition temperature, they are not suitable for fire-retardant applications. Some examples are: Poly
(etheretherketones) (PEEK), poly (phenylene oxide) (PPO) and poly (phenylene sulphide) (PPS).

Chemically, PEEK has a polymer repeat unit of one ketone and two ether groups. Here E signifies ether and K a
ketone segment. Examples of other PEK polymers are PEEKK, PEK, PEKEKK, PEKK etc. This provides a linear,
fully aromatic, highly stable structure containing only carbon, hydrogen and oxygen atoms. It can be melt spun
into an extensive range of monofilaments and fibres.

PEEK fibre-performance, properties and applications:

Applications relate to industrial and technical end-uses where a combination of good physical properties and
inertness to the environment are essential features. The main performance properties are:

Temperature performance : in the temperature range of -60C to 260C.

Chemical inertness : stable to high-temperature steam and most fluids and chemical reagents. Dissolves in
concentrated sulphuric acid (>50%) and degrades by strong oxidising agents such as nitric acid.

Dimensional stability : low creep and low shrinkage.

Polymer purity : fibres are exceptionally pure, without the need for stabilising additives, and they have EEC
and FDA approval for medical 268 high-performance fibres and food-contact use, also has good low surface
energy self-cleaning characteristic.

Flammability : self-extinguishing with an LOI of 35% and lowest levels of smoke and toxic gases emission.

Fibre Products

Starting in the early 1980s, a number of companies set out to produce PEEK fibres of various different types for
commercial sale. Initially, circular cross-section monofilaments in the diameter range 0.4 to 1.0 mm were
extruded at high temperature, cooled, drawn and relaxed to give low shrinkage products with physical properties
in the range 0.3 to 0.4 N/tex tenacity and 30 to 40% extension-to-break, with hot-air shrinkages below 2% at
180 C. By the mid-1980s the polymer quality had improved sufficiently to allow multifilament products in the
range 5 to 15 dtex per filament to be viably produced. These, depending on the process employed, could be
spun with tenacities up to 0.65 N/tex at extensions below 25% and shrinkages below 1% at 180 C. Modulus
values at about 4 to 5 N/tex are typically intermediate between similar polyester and polyamide products. Finer
and heavier monofilaments were also developed, with some specialist products in the 0.2 to 0.3 mm range
having tenacities up to 0.60 N/tex at extensions below 20%, and some of the larger diameter products being
made with higher shrinkages at about 10% so that they could be conveniently heat-set into spiral structures in
subsequent processing. The first crimped filament staple products with a fineness range from 3 to 25 dtex and
staple lengths of 40 to 80 mm were also developed at this time. Finer individual monofils and progressively finer
multifilament yarns down to 100 dtex and filament finenesses of 3 dtex (20mm) have been refined through the
1990s, yielding further improvements in tenacity. Additionally, a wider range of cross-sectional types, including
rectangular and hollow filaments and an increasing range of colour pigmented monofilaments, have become
available for the main monofil diameters (0.20 to 1.50mm). The manufacturer with the most comprehensive
range of PEEK fibre products through this period has been ZYEX Limited.19 Other producers, such as Teijin,
Kosa, Shakespeare, Luxilon and Albany International, have chemically resistant fibres 269 at different times
been active in different segments of the PEEK fibre business but none other than ZYEX has yet attempted to
cover more than a small part of the potential product range.

Fibre Properties

The value of PEEK fibre products does not normally lie in their measured starting properties or with their short-
term performance. As has been indicated, PEEK monofils, yarns and fibres are in fact similar to polyester or
nylon products in these respects. It is rather PEEKs ability to retain useful properties at an extreme condition or
throughout an extended working life that differentiates it from mainstream industrial fibres. The thermal,
chemical and abrasive endurance of PEEK sets it apart from comparable industrial fibres, as is indicated in the
following tables. This is especially true in real industrial processing situations where a combination of these
factors, rather than just one, may be causing standard materials to fail prematurely. Table 4 shows the
resistance to hot air exposure over a 28-day period, and Table 5 the ability of PEEK fibres to withstand steam
for 7 days. Clearly, PEEK can perform well at temperatures up to 300 C in both dry air and steam, thus
indicating its oxidation and hydrolysis resistance

Table 2. Chemical resistance of PEEK fibres at various temperatures


Chemical 23C 100C 200C
Acetic aid,10% A A
Carbonic acid A A
Citric acid A A
Formic acid B B
Hydrochloric acid,10% A A
Nitric acid A A
Nitric acid, 30% B
Phosphoric acid, 50% A A A
Sulphuric acid, <40% B B B
Ethanol A A A
Ethylene glycol A A B
Ethylene glycol, 50% A A A
Acetone A A
Formaldehyde A A
Methylethyl ketone(MEK) A B C
Ammonia, aqueous A A A
Sodium hydroxide,50% A A A
Aluminium chloride A A
Carbon monoxide(gas) A A A
Ferric chloride B B
Hydrogen sulphide (gas) A A A
Iodine B
Ozone A B
Phosphorous pentoxide A A
Potassium bromide A A
Sulphur dioxide A A B
Carbon tetrachloride A
Chloroform A
Trichloroethylene A
Aromatic Solvents A
Benzene A A
Brake fluid(mineral) A A
Dowtherm ht B
Methane (gas) A A
Motor oil A A
Naphthelene A B
Oils(petroleum) A A
Dimethylsulphoxide(DMSO) B B
Diphenylsulphone(DPS) B C C
Poly(phenylene sulphide), PPS (ARH)
Its chemical structure has an aromatic backbone. Therefore polymerization to high molecular weight and
spinning are challenging.

PPS fibres have an acceptable balance of properties for many end-uses in terms of tensile properties under dry
and wet conditions. The applications at high temperatures depend on the levels of applied stress during service;
obviously for high stress end-uses, the second order transition temperature will define the upper useful limit,
whereas in lower stressed applications, such as gas filtration bags, long-term exposures above 180 C are
possible. These fibres can also withstand temperature up to 230 C for very short periods. Experimental
exposures to hot air shows that PPS fibres retain 60% of their original strength after 1000 hours, at 260 C and
90%, 70% and 60% retention after 2000, 5000 and 8000 hours, respectively at 204 C. The relatively high LOI
of 3435% indicates an acceptable level of inherent flame resistance. However, the general ease of oxidation of
the sulphur atom present in the polymer chain is indicated by this value being less than observed for PPO fibres
(LOI = 68%) and the susceptibility of PPS fibres to oxidising agents. During light exposure it is discoloured but
compares favourably with poly (meta-aramid) fibres in terms of retention of tensile properties.

Table 3. Physical Properties of PPS Staple & Monofilament Fibre


Property Staple Monofilament
Tenacity (N/tex) 0.27-0.47 0.27-0.37

Tenacity retention (%)


at 100 C 70 -
at 150 C 58 -
at 200 C 52 -

Knot tenacity (N/tex) - 0.18-0.23


Breaking strain (%) 25-35 12-16
Initial modulus (N/tex) 2.7-3.7 4.1-5.0
Elastic recovery (%)
at 2% strain 100 -
at 5% strain 96 -
at 10% strain 86 -
Boiling water shrinkage (%) 0-5 -
Moisture regain (%) 0.6 -
Specific gravity (g/cm )3
1.37 1.37
Melting point (C) 285 285
Colour golden golden
Limiting Oxygen Index (%) 34-35
Auto Ignition Temperature ( C) 590 -
93 (high stress)
Maximum Service Temperature 93(high stress)
182-190 (low stress)
(C) 182-190 (low stress)
232 (surges)

The excellent chemical resistance of these fibres is demonstrated in Table 4. Resistance to non-oxidising acids is
excellent, as is that to hot alkalis, thereby showing that in spite of PPS being a condensed polymer, it has
considerable resistance to hydrolysis. However, the sulphur in the main chain is vulnerable to oxidizing conditions
therefore it has reduced durability on exposure to oxidising agents. It shows varying resistance to organic
solvents.

It is used for battery separators and filter cloths (as felts or woven constructions) for filtering hot, corrosive
chemicals such as organic chemicals, acids and bases. Sewing threads for use in these products are also valid
applications.

Poly(ether imide), PEI


Like PEEK, poly(ether imide) fibres are also used in some applications where chemical and temperature
resistance are required. Although its temperature resistance is slightly inferior to that of PEEK, PEI is a cheaper
material.
PEI is essentially an amorphous polymer and can be melt-spun to result in fibres having only moderate tenacities
(0.25N/Tex) and breaking elongations of about 40%. PEI fibres can resist temperatures up to 190 C for long
periods and also possess high LOI value of 45%, which is higher than the values for PEEK and PPS. A comparison
of the properties of PPS, PEEK and PEI is presented in Table 4, 5 & 6.

Their high LOI value indicates stability at high temperatures and resistance to oxidation and so they are used in
hot gas filtration applications, especially where aggressive chemical environments are present. These fibres have
very good resistance to dilute acids and alkalis although resistance to concentrated acids is poor. Resistance to
organic species is variable and may be poor for aromatic solvents and vapours.

Table 4. PEEK and other fibres exposed to elevated temperatures for


28 days in air

Fibre % Strength retained

Temperature 150C 200C 250C 300C


PEEK 100 100 95 90
m-aramid 100 95 75 0
PPS 100 90 0 melted
PET 90 30 0 melted

Table 5. PEEK and other fibres exposed for 7 days in pressurised steam
Fibre % Strength retained

100C 150C 200C 250 300


Temperature
PEEK 100 100 100 95 80
PPS 100 100 90 0 disintegrated
m-aramid 100 95 0 0 0
PET 90 0 0 0 disintegrated

Table 6. Cycles to failure for PEEK and other fibres as threads-


thread on thread abrasion at 120 C loaded at 0.05 cN/tex
Fibre Cycles of Failure
PEEK 900
PA 600
PET 500
m-aramid 250
PPS 50

Other fibres in this group include the polyaramids (both meta- [e.g. Nomex, DuPont] and para-derivatives
[Kevlar, DuPont; Twaron, Acordis]), polyarimid [P84, Inspec Fibers], poly(aramid-imide) [Kermel,
Rhodia],poly(benzimidazole) [PBI, Celanese] and the oxidised acrylics [Panox, RK Textiles/SGL UK]. These are
primarily used as high temperature fibres and have been discussed in the previous lecture.

Copyright IIT Delhi 2009-2011. All rights reserved.

MODULE 4. INORGANIC FIBRES


4.1 Glass Fibres (2 Lectures)
As per American Society for Testing and Materials (ASTM), a glass is an inorganic product of fusion which has
cooled to a rigid condition without crystallization.

Contradicting the general definition of high performance fibres, the glass fibre has an isotropic three-dimensional
network structure and is not crystalline.

Drawing of Glass is an ancient technology

Winding coarse glass fibres onto clay mandrel was used to make vessels
In the 1700s, Raumur recognized that glass could be finely spun into fibre that was sufficiently pliable to
be woven into textiles.
Napoleons funeral coffin was also decorated with glass fibre textiles.
Glass fibre dress was first made in 1893 by Edward Drummond Libbey
Glass fibre dress was first time worn by actress Georgia Cayvan.
The first commercial production of glass fibre started in 1936.

Glass Chemistry, Composition and Types

The main constituent of glass is silica (SiO ).Silica melts at very high temperature i.e. 1713 C. Secondly, it
2

rapidly crystallizes on solidification and forms a regular structure. Both these factors pose a difficulty in
processing of glass. The limitation of high melting temperature is overcome by addition of impurities to silica.
This causes a depression in melting point. Secondly, if the melt is cooled very rapidly, the melt thickens and
molecules are arrested/ fixed in a random state before the regular arrangement takes place. This takes care of
the second problem. This concept is used in the manufacture of glass, for example: addition of 25 % soda (Na O) 2

lowers the liquidus temperature of silica from to 1713 C to 793 C and lowers its viscosity substantially. Let us
understand this qualitatively if we imagine the soda rich structure. This structure is more tightly packed with
atoms (has higher density), but actually has lower network density in three dimensions because fewer oxygen-
silicon links (as shown in Figure 1 ). Therefore has a lower liquidus temperature.

Such additives, which are used in production of glass to lower melting temperature, inhibit
crystallization and control fluidity are called modifiers/fluxing ions.

a b
Figure 1 Schematic showing a)crystalline network of ceramic and b) amorphous network of glass
Therefore depending on their formation, the oxides used in glass composition can be classified as glass formers,
intermediates or modifiers. The glass formers are those elements whose oxides will form a glassy structure.
Silica or silicon dioxide (SiO ) is the most frequently used glass former but the oxides of boron (B O ), germanium
2 2 3

(GeO ), phosphorous (P O ), vanadium (V O ) and arsenic (As O ) are also used to form glasses. Intermediates
2 2 5 2 5 2 3

may act as glass formers in some compositions and as modifier/fluxes in others. Aluminium oxide (Al O ), 2 3

antimony oxide (Sb O ), lead oxide (PbO) and zinc oxide (ZnO) are intermediates. The modifiers as explained
2 3

above will form a mixture having a lower melting temperature than the glass formers alone. Modifiers include
calcium oxide (CaO), sodium oxide (Na O), potassium oxide (K O), barium oxide (BaO) and lithium oxide (Li O).
2 2 2

Because the commonly used alkali oxides tend to produce glasses of low chemical stability or devitrification
resistance or both, alkaline earth oxides are usually required as stabilizers. For instance, the combination of silica
sand as a glass former and sodium oxide as a flux will produce a glass, but this composition is a rather
disappointing glass since it dissolves readily in water. Adding calcium oxide as a stabilizer improves chemical
durability and produces a type of glass known as soda-lime glass, the kind used for windows and bottles. Other
ingredients may be added to improve manufacturing efficiency or to produce a particular property. Some of the
compositions of glass contain as many as ten ingredients; some of the well known glass compositions (values in
wt%) are listed in Table 1.

Table 1. Compositions of Different classes of Glasses

SiO 2
Oxides (wt%)
Type/Composition Property
(wt%) Al O CaO MgO Na O others
2 3 2

AR-Glass ZrO 2

62.2 0.74 5.2 0.16 14.3 Resistant to alkali


Soda lime silicate glass 16.7
C-Glass BO
3 3 Chemically stable in corrosive
65 4 14 3 8.5
Calcium borosilicate glass 5 acid environment

E-Glass
BO
3 3 High strength and electrical
Alumina-calcium- 55.2 14.4 18.7 3.3 0.3
7.3 resistivity
borosilicate glass
S-Glass High strength, modulus and
Magnesium 65 25 10 stability under high
aluminosilicate glass temperatures

Bulk of the glass used for large scale applications like glazing and bottles is sodalime glass. Glass fibres have
been produced using many different compositions of mineral glasses. The most common are E glass, C glass and
S glass. E (electrical) glass is the most commonly used because it draws well and has good strength, electrical
and weathering properties. C glass has a higher resistance to chemical corrosion than E glass but is more
expensive and has lower strength. S (strong) glass is more expensive than E glass but has higher modulus and
strength and is more temperature resistant. It is used in special applications such as the aircraft industry where
the higher modulus may justify the extra cost.
Glass manufacture:

In this stage mixing and fusion of raw materials is carried out in a batch furnace at a temperature of about 1700
C to form a homogeneous glass. The glass manufacturing can end either with the liquid glass flowing directly to
fibre forming furnaces called bushings or the glass is formed into marbles or rods, annealed and cooled at
room temperature for further use.
Figure 2. Production of Glass Fibre
Formation of Glass Fibre:
The glass fibre production process can be one stage, direct melt or continuous when stages A and B are
integrated. The molten glass, is fed into a series of electrically heated platinum bushings each of which has
several hundred holes in its base. The glass flows under hydrostatic pressure (i.e. weight of the glass melt
column above the nozzle) and fine filaments of 8-15 micron average final diameter are drawn mechanically
downwards at speeds of 1000 metres per minute or more. The viscosity of the glass melt, the hydrostatic
pressure, the diameter and length of the nozzle and the winding speed are the most important parameters which
determine the diameter of the drawn glass fibre. The fibres are immediately cooled by sprayed water at the
bushing, coated with a size, assembled into a strand and wound to produce a cake. The size (or finish) is crucial
to the handleability of the fibres and their compatibility with the matrix. The size is chosen to suit the application
or further processing. The finish consist of:

an adhesion promoter or coupling agent,


a protective polymeric size or film former,
lubricant(s),
surfactant(s),
antistatic agent(s), and
an optional polymeric binder (emulsion or powder) used for fibre mats.

The Coupling Agent


The coupling agent plays a key role in a composite and provides a proper adhesion between the fibre and the
matrix so that the stress is transferred efficiently. Typical coupling agents used for glass fibre resin adhesion are
as shown in Figure 3 :
Figure 3. Typical Coupling agents used for Glass-Resin adhesion
The above mentioned silanes have the following structure

In aqueous solution in the presence of acetic acid (used to adjust the pH of the sizing emulsion), the alkoxy (RO)
groups hydrolyse and polymerise to give linear and branched poly (hydroxy siloxane).These structures form the
interphase between the fibre and resin and improve adhesion.

Figure 4. Typical Coupling agents used for Glass-Resin adhesion


Formation of Glass Wool:
For making a glass suitable for various insulation and composite based applications, rotary spin process shown in
Figure 5 is used. The wool fibre glass mat is coated with the binder and cured. The cure mats are used for
various applications in composites.
Figure 5. Rotary Spin Process
Optical Fibres :
The commercial optical fibres based on silica glass core-clad structure, are made as a bulk preform and drawn
down into an optical fibre of diameter 125 mm, as shown in Figure 6. Ge, P and B are introduced as dopants to
give the required refractive index profile, viz a core of approximately 8 mm diameter with a refractive index
enhancement of 0.001 to give a monomode fibre. The efficiency of light transmission depends on the wavelength
of light employed. Pure fused silica has low loss windows at 1.3 and 1.5 mm with transmissions. The cable based
on glass optical fibre has higher data capacity than conventional copper

Figure 6. Glass Fibre drawing from Bulk Preform


Properties and Applications of Glass Fibres:
Glass is an amorphous material having micro-heterogeneous structure with 3-D atomic bonding without any long
range order or orientation. The strength and modulus of glass are determined primarily by the three dimensional
structure of the constituent oxides. Consequently, the glass fibres have a unique characteristic, viz. they are
isotropic with the mechanical properties along the fibre axis being the same as transverse to the axis. The
modulus and strength of glass fibres are lower than the other high-performance reinforcing fibres, however the
elongation-to-break is relatively high. Glass fibres have high temperature resistance and low thermal expansion
and are inexpensive. However, they are very brittle.

Table 2. Physical properties of different classes of Glass Fibres

C-Glass E-Glass AR-Glass S-2 Glass


Density (gm/cc) 2.52 2.58 2.70 2.46
Refractive index 1.533 1.558 1.562 1.521
Softening point, C 750 846 773 1056
Annealing point, C 588 657 816
Textile Strength (MPa) at 3310 3445 3241 4890
23 C
Young's Modulus (GPa) 68.9 72.3 73.1 86.9
23 C
Elongation % 4.8 4.8 4.4 5.7

Glass fibres have been used as reinforcements in a variety of applications which include reinforcement of
thermoplastics and their use in various appliances and in motor cars, reinforcement of rubber tyres,
reinforcement of underground petrol storage tanks made from plastics and reinforcement of plastics. Glass fibre
is also an attractive additive to cement for improving the flexural strength of the cement composite. The
development of sheet moulding compound (SMC) and dough moulding compound (DMC), which are pre-mixed,
easily handleable mixtures of fibre and unsaturated polyester resin, allow the mechanisation of composite
moulding process via matched die moulding or injection moulding.

Though `E' glass is now the most extensively used fibre as reinforcement in composites, it has one limitation,
viz. it dissolves in dilute mineral acids. For this reason, for composites which are likely to come in contact with
acidic materials, a protective layer of corrosion-resistant `C' glass is often used in fibre form. For high strength
applications like rocket motor cases, S glass may be used.

The low thermal conductivity or sound transmission ability of fibrous wool is important for insulation applications.
A-glass fibres are used as insulants in thermal or acoustic applications. E-glass fibres are also used in fire
resistant textiles, which can be coloured using dyeable sizing. The thermally resistant property of glass is also
made use of for filtration. The other major and growing application is SiO -based glass for optical fibre
2

communications.

Copyright IIT Delhi 2009-2011. All rights reserved.


MODULE 4. INORGANIC FIBRES
4.2 Ceramic Fibres (2 Lectures)
What are ceramics?

The definition of ceramic is often restricted to inorganic non-metallic polycrystalline solids, as opposed to the
noncrystalline glasses. The distinction between ceramic and glass has become difficult now, because ceramics
produced from new precursors or sol gel routes can be amorphous. Figure 1 shows a general classication of
non-metallic inorganic bres including ceramic bres.

Figure 1. Classification of non-metallic inorganic fibres


First ceramics were the pottery objects made up of clay and were developed for refractory insulation. Traditional
ceramic has kaolinite as clay mineral that is an alumina whereas modern ceramics include silicon carbide,
tungsten carbide and many more. Silicon carbide and aluminium oxide (alumina) fibres are commercially being
produced, while several other ceramic fibres are either being made on pilot scale or are under various stages of
development.

Ceramic materials are hard, have low densities (compared to metals), high compressive strength and very good
thermal resistance and strength at higher temperature. Due to their notable high temperature performance,
these are useful as reinforcement in metal and ceramic matrix composites, where the structures are required to
operate at high temperature and under oxidizing/ corrosive environments, examples: in- heat exchangers, first
containment walls for fusion reactors, gas turbines, as well as for high temperature gas filtration.

The low strength of these materials is significantly increased when the ceramics are in the form of fine filaments
composed of sub-micron grains. The requirements for high-performance reinforcements would therefore be
fulfilled if such bulk ceramics were transformed into fibres.

How are ceramics fibres produced?


Conventional processes for the fabrication of bulk ceramics, which include powder compaction and sintering,
cannot be used for making fine fibres. Also, the conventional spinning and drawing from a melt cannot be used
for ceramics as their melting points can exceed 2000 C.

Figure 2 Sintering process of producing objects from particles


The ceramic fibres can be produced by either a direct or indirect process.

Direct Process

The direct production of fine ceramic fibres requires the spinning of precursors (salt solution, sols or precursor
melts) into fibres, which are then heat treated and pyrolysed for a very short time. The first ceramic fibres for
very high temperature structural applications were commercialised at the beginning of the 1980s and, since
then, the fibres have undergone great changes and shown improved properties.
Figure 3. Direct method for obtaining ceramic fibres
The spinning dopes used in the direct process can be based on:
Molecularly dispersed precursors
Colloidally dispersed precursors
Inorganic polymers
Coarse ceramic particles

Indirect method

On the other hand the in indirect process, ceramic fibres are not obtained by spinning process, but by using
some other approach. The process involves two steps:

Step 1: Organic substrate/template fibres are soaked with the precursor material or precursor material is
deposited on the surface.

Step 2: The inorganic fibre is then formed by pyrolysis of the organic template fibre.

Figure 4. Indirect method for obtaining Ceramic Fibre


Chemically these fibres have different compositions and thus these fibres can be broadly divided into following
two categories:

Oxide fibres : Silica fibres, alumina fibres, alumina-silica fibres, alumina zirconia fibres
Non oxide fibres: Silicon carbide(SiC),silicon carbon nitride, silicon nitride(SiN)

Oxide Based Fibres

Oxide ceramic fibres made from oxides with high melting point are suitable for applications where exposure to
oxidizing atmosphere and high temperatures (above 1400 C) are required.

Oxide fibres, currently available commercially are mostly based on Al O or Al O /SiO ceramics. They possess
2 3 2 3 2

high tensile strength and modulus, and are stable against oxidation at high temperatures due to their oxidic
nature. However, even the best polycrystalline oxide fibres are prone to creep under load at 1100 C. These
fibres tend to form larger grains when kept at high temperatures over long time periods. The larger grains tend
to grow at the expense of smaller grains because of diffusion processes at grain boundaries, which can lead to
brittle fibres.

Alumina-based Fibres

Alumina fibre is used in various applications which include high temperature insulating material in the form of
mats, blankets and boards, fire protection, catalyst support in high temperature reactions and as reinforcement
of metals, ceramics and polymers.

In one method alumina fibre is made by extruding aqueous solution of aluminium salts such as aluminium
oxychloride (Al (OH) Cl) blended with rheological aids. The alumina fibre is made by spinning and heat treatment
2 5

route. The aqueous nanosols based on aluminium hydroxides can also be spun directly. Simple molecular
precursors are converted into nanometer-sized particles to form a colloidal suspension, or sol. In order to assist
the spinning process, the sols are made more concentrated and viscous by the addition of a small amount of
organic polymer which would cause an increase in the viscosity This sol is spun into the gel fibre, which is dried
and sintered to form the required ceramics.

At temperatures higher than 400 C and up to around 1000 C, the formation of grains of 10 to 100 nm, size is
formed with finely divided porosity. Above 1100 C, stable -alumina nucleates resulting in fast growth of
micron-sized grains together with the coalescence of pores. Such fibres are extremely brittle and cannot be
used. For use of alumina fibres above 1100 C, the nucleation, growth and porosity are controlled by adding
either silica precursors or seeds for -alumina formation to the fibre precursors and has led to two classes of
alumina-based fibres, one consisting primarily of -alumina grains and the other of transitional alumina phases
together with another phase.
Figure 5. Process steps for manufacture of alumina fibre

Figure 6. Preparation of Ceramic fibres


Table 1. Some properties of ceramic fibres
Young's
Composition Diameter Density Strength Strain to Modulus(GPa)
Fibre type Manufacturer
(wt%) (m) (g/cm ) (GPa) failure(%)3

-Al O fibres
2 2 Du Pont 99.9% Al O 2 3 20 3.92 1.2 0.29 414

85% Al O2 3

Aluminia silica fibres 3M 12 3.4 2.1 0.81 260


15%SiO 2

Non-Oxide Ceramic Fibres :

Non - oxide ceramic fibres are based on SiC and Si-C-(N)O materials. Fibres exhibit high values for tensile
strength and modulus higher than oxide fibres and due to their structure, which is amorphous in many cases,
they have lower creep rates at high temperatures when compared to the polycrystalline oxide fibres.
Disadvantages of these fibres are their susceptibility to oxidation, which leads to fibre degradation in an oxidizing
atmosphere over time. The lower the oxygen content of the fibre itself, the better its oxidation resistance.

Silicon Carbide-based fibres


Spinning and heat treatment :

Silicon carbide (SiC) fibres are commercially produced under the trade name of Nicalon TM, by melt spinning of
organosilicon polymers such as polydimethyl silane. The meltspun filament is heated in the air to 190 C to
crosslink the polydimethyl silane molecules by oxygen and then heat treated at 800-1500 C in nitrogen or
vacuum to form crystalline structure. During heat treatment, hydrogen and methane gases are evolved at ~ 700
C and the silicon carbide fibre is formed as per the following scheme

Crosslinked poly dimethyl silane [SiC+CH +H ] 4 2

The conversion to ceramic fibres occurs by pyrolysis above 1200 C. The choices of the precursor polymers and
of the crosslinking processes have a great influence on the final composition and microstructure of the ceramic
fibres.

By chemical vapour deposition:

Both tungsten and carbon cores are used as templates for making silicon carbide fibres by CVD route. In
commercial production, the gas mixture is introduced at multiple injection points of the vertical reactor. The
temperature along the reactor passes through a maximum between 1400 and 1500 C at an early stage of
deposition. Passage through the reactor is of the order of one or two minutes and results in a fibre with a
diameter greater than 100mm.Various carbon-containing silanes have been used as reactants. In a typical
process, with CH SiCl as the reactant, SiC is deposited on the core as follows:
3 3

Various non-oxide fibres have been developed at a laboratory or pilot scale from other silicon containing
precursors such as polysilazane. The fibres obtained have amorphous structures based on SiCNO, SiN or Si
BNC, but recrystallise from 1200 C or show poor oxidation resistance. Boron nitride fibres with oriented
turbostatic structures are also being developed for specific applications, but they are intrinsically not adapted to
resist oxidation.

Copyright IIT Delhi 2009-2011. All rights reserved.


MODULE 5. OTHER SPECIALITY FIBRES
5.1 Elastomeric fibre (2 Lectures)
What are Elastomeric Polyurethane Fibres ?
According to ASTM definition: An elastomeric material is one which at room temperature can be stretched
repeatedly to at least twice its original length and upon immediate release of stretch, will return with force to its
approximate original length.

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

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

Relaxed/coiled state
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.

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

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

The term polyurethane is used to describe polymeric materials with predominant urethane linkage

[-NH-CO-O-]
The fibres that meet the molecular requirements for rubberlike threads and are based on polyurethanes are
categorized as elastomeric polyurethane fibres. Interestingly, the first polyurethane fibre spun in Germany was
not an elastic yarn but was an ordinary hard yarn, rather like nylon. It was made by reacting 1,4 butanediol
with hexamethylene diisocyanate, the two adding together to give the polyurethane. This polymer was entirely a
polyurethane unlike the current elastomeric fibre.

nButane diol + hexamethylene di-isocyanate = polyurethane

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

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

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

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

Figure 1. Polyurethane Linkages


Chain Extension

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

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

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

One example of elastomeric fibre is Spandax fibre. Lycra or spandex was developed in 1959 by Dupont. It is a
copolymer of high molecular weight poly tetra methylene glycol or caprolactone or polyethylene adipate as soft
segment and diphenylmethane-4,4-diisocyanate or toluene-2,4-diisocyanate as hard segment.
Chemical Structure of diisocyanates:
Chemical structure of some polyols: In general the soft segment has a very low melting point,if any,and is
based 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
Chemical structure of some chain extension agents:
H NCH CH NH
2 2 2 2

Diethylamine

H NNH 2 2

Hydrazine

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

In the normal wet spinning, the solution is extruded into a coagulation bath through a spinneret and after
coagulation, combination and fusion between the filaments take place, the fibre is wound up. The spinning of
prepolymer is known as reaction spinning.
Figure 3. Different routes for polyurethane spinning
Dry spinning
The majority of elastomeric fibres made by solution spinning are dry-spun products having a polether urethane
structure. The dry spinning dope, containing at least 25% polymer, is metered through a filter pack and
spinnerets at the top of a vertical spinning tube at required temperature. In the presence of heated inert gas
flowing through the cell, nearly complete removal of solvent occurs as the filaments descend through the cell
and becomes thinner. Unlike most synthetic fibres, these fibres are not subjected to an extensional drawing
stage but are used in as-spun form. After emerging from the tube, the fibre is twisted. The twist travels
upstream along the fibre to a point in the upper part of the tube where the filaments comprising the fibre fuse
together and form an aggregate of filaments. This fusion is indispensible for subsequent processing of the fibre
to prevent damage. The twist imparted is removed by the time the fibre reaches the first roller by means of the
tension of the fibre itself. Then the finish oil that includes anti-tack agents is applied by contact with the finishing
roller to prevent yarn adhesion on the package and is wound up by way of second roller. As shown in the Figure
4, the heated gas is supplied perpendicular to the fibre as in melt spinning. This prevents gas turbulence and
heat transfer fluctuations. Therefore accelerates the solvent evaporation and decreases the entanglement of
fibres and denier fluctuations.

Figure 4. Dry spinning of polyurethane


For increasing the spinning speeds, the main controlling parameter is the solvent evaporation rate. Therefore, for
increasing 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)
Reaction Spinning:

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

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

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

Melt Spinning

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

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

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

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

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

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

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

Figure 6. Schematic representing hard and soft segments of elastomer


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

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

At ~ 500 % extension, this process is complete and treatment of extended sample with warm water (80 C)
results in uniform distribution of forces amongst soft segment chains. This causes a loss of elongational
crystallization. On relaxation the soft segments disorient completely, while the hard segments tend to remain in
oriented form.

The various mechanisms of hydrogen bond disruption or physical relaxation in hard segments are shown
schematically Figure 7.

Figure 7. Mechanism of hard bond disruption & relaxation


in hard segments
Copyright IIT Delhi 2009-2011. All rights reserved.

MODULE 5. OTHER SPECIALITY FIBRES


5.2 Lyocell Fibres (2 Lectures)
The regenerated cellulose fibre is produced by derivatizing cellulose in CS or in cupraammonium and by
2

subsequent spinning and coagulation. In both these processes environmentally hazardous by-products are
formed (CS , H S etc.). However, if the cellulose can be dissolved without derivatization, the problems associated
2 2

with derivatization and regeneration can be avoided, resulting in reduced environmental pollution and chemical
waste generation. Alternate processes using direct dissolution of cellulose have been studied. Some of the
suitable solvent systems are:

N -methylmorpholine N-oxide /water (NMMO/H O) 2

Lithium chloride/dimethyl acetamide(LiCl/DMAc)


Trifluroacetic acid/dichloroethane (TFA/CH Cl ) 2 2

Calcium thiocyanate/water(Ca(SCN) /H O)
2 2

Ammonia/ammonium thiocyanate(NH /NH SCN) 3 4

Zinc chloride/water(ZnCl /H O)
2 2

Sodium hydroxide/water(NaOH/H O) 2

The most promising of these solvent systems, which has been commercially exploited, is the amine oxide /water
system (NMMO/H O). 2

Cellulosic fibres produced using this organic solvent spinning process are known as lyocell fibres. These are also
known as Tencel.

Lyocell Process

The use of N -methylmorpholine N-oxide (NMMO) as a solvent in lyocell process is advantageous as


derivatization or xanthation is not required. Also, the process requires very few chemicals (NMMO and water),
which are completely recyclable. The main advantage of NMMO solvent is that it is biodegradable and is non-
toxic. Hence the process is environment friendly.

Mechanism of dissolution in N-methyl morpholine oxide( NMMO)

N-methyl morpholine oxide (NMMO) is a cyclic, aliphatic, tertiary amine oxide.

Figure 1. Structure of N-methyl morpholine oxide (NMMO)


NMMO is a highly polar organic amine with N-O bond having a dipole moment, as shown in the Figure 2. Due to
its highly polar nature it can form hydrogen bonds with the hydroxyl groups of cellulose and has extremely high
solubility in water. A competing reaction takes place between water and cellulose for NMMO molecules and water
being a smaller molecule is preferred. These properties are the basis for its use as cellulose solvent.
Figure 2. Polarity of NMMO
NMMO is a strong oxidizer and a very corrosive solvent. Pure NMMO melts at 170 C. At temperatures higher
than 150 C, NMMO can undergo highly exothermic decomposition reactions. Therefore, pure NMMO melt cannot
be used as a solvent for cellulose.

NMMO mono and dihydrate melt at 74 C and ~35 C respectively. Therefore, water content and temperature of
NMMO play an important role in dissolution of cellulose. NMMO hydrates of required composition or NMMO/water
can be used as a possible solvent and relatively homogeneous cellulose solutions can be prepared only with
relatively, minor amounts of water.
Manufacturing of lyocell fibres

The process for manufacture of lyocell is much shorter than that for viscose, where the need for various ageing
stages extends the process time to more than 40 hours. The main steps for lyocell fibres manufacture are shown
in Figure 3. The process involves:

Preparation of the dope of the starting cellulose (dissolving pulp) in an NMMO- water mixture.
Extrusion of the highly viscous dope at elevated temp through an air gap into a precipitation bath (dry-jet
wet spinning)
Coagulation of the cellulose fibre in the precipitation bath
Washing, drying and post-treatment of the cellulose fibre
Recovery of the NMMO from the precipitation and washing baths.
Figure 3. Flow chart showing key stages in the manufacturing of lyocell fibres
Dope Preparation
For preparation of spinning dope, a 5060% aqueous NMMO is used for making a slurry of cellulose pulp. In a
typical process, the slurry is produced from cellulose pulp and an aqueous NMMO solution. Typical compositions
used for this are 5060 %NMMO, 2030% water, and 1015% pulp. Addition of 0.010.10% antioxidant n-
propyl gallate (PG) is desirable for preventing degradation of cellulose.

Subsequently, excess water is removed by evaporation under reduced pressure and at temperatures lower than
150 C till the cellulose is dissolved and a homogeneous solution is formed.

A typical isotropic spinning dope composition contains 14% cellulose, 10% water, and 76%
NMMO.Temperatures between 90-120 C are used.

As shown in the Figure 4, the solubility of cellulose in the aqueous NMMO solution depends on water content.

Usually aqueous NMMO solutions containing more than 1517 wt% water do not dissolve cellulose. At such high
concentrations (>17 wt%) of water, NMMO forms hydrogen bonds with water and is not available for interaction
with cellulose hydroxyl groups. This prevents the dissolution of cellulose.

At lower concentrations of water, oxygen of N-O can form hydrogen bonds with cellulose hydroxyl groups and the
dissolution can occur. At water concentration lower than 4 wt%, the dissolution temperatures are very high
(close to degradation temperature of cellulose). Therefore 4 wt% is considered as the lower dissolution limit.

Figure 4. 3-Phase diagram showing the composition for Dope formatio


Typical, safe processing temperatures are in the range of 80130 C. Cellulose dissolution increases with
increase in temperature and input of mechanical energy, while it decreases with increase in water content,
concentration and DP of cellulose.

In case of lyocell, no ripening step is involved, therefore, the pulps used for NMMO processing usually have
slightly lower DP (molecular weight) than that of viscose process.
Anisotropic cellulose solutions can be obtained if the water content is below 11% thus indicating that some water
from hydrated NMMO molecules must be released. High-modulus, high-strength fibres from concentrated
anisotropic cellulose dopes with a molar ratio of NMMO to water of less than one can be obtained. Obviously, the
viscosity of cellulose anisotropic solutions is strongly dependent on the concentration and DP of cellulose pulp.

Fibre Formation

Figure 5. Schematic of Fibre formation process

The spinning of ternary solutions of cellulose-NMMO-water is carried out at elevated temperatures ranging from
90-120 C. The fibres are produced by using a dry-jet wet-spinning process in an NMMOwater solution. Air gaps
vary from 20 to 250 mm. Although, it is claimed that NMMO is non-toxic and biodegradable, it is very expensive,
and a closed loop process has been developed and nearly 99.5% of the NMMO is recovered and can be reused.

The molar ratio of NMMO to water is close to 1:1. The spinning speeds of about 100 m/min. are used. A higher
speed tends to improve final fibre orientation and depends on the air-gap length. The final properties of Lyocell
fibres depend on a number of variables that are grouped in Figure 6. As shown in the figure, the final fibre
strength will depend on the properties of spinning dope, spinning conditions, coagulation condition, and post-
treatment conditions.
Figure 6 : Process variables in lyocell process
The Structure Formation

During spinning process, the structure formation is determined by concurrent orientation, coagulation and
crystallization processes. The crystallization is affected by solution characteristics, the precipitation conditions,
and drying / post treatment conditions. All these processes are interdependent.

During the shear deformation in the nozzle and in the air gap, it is proposed that orientation of the polymer
molecules is similar to liquid crystal polymers occur. The relatively long relaxation times are expected to help in
preserving the oriented state in the air gap.

In the coagulation bath series of steps are reported to occur:

The exchange of solvent against non-solvent (e.g. water) and desolvation of cellulose molecules.
Diminished interaction between the cellulose and solvent.
Increased interaction between NMMO water
Oriented cellulose interact with each other
Phase separation(fast process)
Desolvated polymer chains laterally connected with needle like voids, filled with NMMO-water
With increasing water content in the cellulose-rich phase the laterally connected lamellae start to
crystallize building up a fibrillar network.

So, one can conclude that the voids originate from the precipitation process and not from an incomplete
densification of the fibrillar elements during drying.

Properties and Applications of Lyocell Fibres

Lyocell fibres have very different structural properties than that of viscose. The DP of cellulose in Lyocell fibres is
~ 600, which is about twice that of viscose fibres.

Lyocell fibres are more crystalline and more oriented than viscose fibres. NMMO -type fibres have a circular
cross-section which is markedly different from the lobulated shape of textile viscose fibres. They have an oval or
round shape ( Figure 7a ) with smooth surface and tend to be highly fibrillar on the other hand, viscose fibres
exhibit skincore morphology and are more porous (see Figure 7b ).

Figure 7. Cross-section of a) Lyocell Fibre and b) Viscose Fibre


Due to these structural features, lyocell fibres have a greater tenacity and greater wet strength than viscose
fibres.
The main properties of Lyocell fibres in comparison to other cellulosic fibres are summarized below in Table 1
Table 1 : Main properties of Lyocell fibre and other cellulosic fibres
Lyocell Viscose HMW Polynosic Cotton
Average DP ~600 ~300 ~400 ~500 1600-2000
Water retention, % 65 90-100 75 55-70 50
Tenacity, 65 % RH and 20 C,
36 25 45 38 20-24
(cNtex )
-1

Tenacity, wet(cNtex )-1


29 13 30 30 26-28
Elongation, 65 % RH and 20 C,
14 20 12 8 7-9
%
Elongation, wet,% 16 23 15 9 12-14
Lyocell Fibre vs Regenerated Viscose

The peculiarities of Lyocell fibres like:

high crystallinity
long crystallites,
high degree of orientation,
well oriented amorphous regions
result in a very high dry and wet tensile strength, a high wet modulus and high loop tenacity. The high
amorphous orientation prevents a sufficient lateral cohesion and thus results in fibrillation effect.
The fibrillation is useful for manufacture of non-woven technical products and composites.Since fibrillation is not
always desirable property, Lyocell fibre is cross-linked using multifunctional crosslinkers.
Modified lyocell fibres can be produced by incorporating chitosan and/or nanomaterials such as silver, ZnO or TiO 2

in the spinning dope to impart various functionalities, such as odour-reducing and antibacterial properties.

The main applications of lyocell fibres are in:

Adhesive Substrates
Battery Separators
Electrical
Filtration Media
Food Casings
Flushable Papers
Glass Fibre Binder
Insulation Papers
Medical Papers
Napkins, tablecloths, tissues
Reinforcement papers
Security / Banknote Papers
Tea Bags

Copyright IIT Delhi 2009-2011. All rights reserved.

MODULE 6. FIBRES FOR MEDICAL APPLICATIONS


6.1 Biodegradable Fibres (2 Lectures)
Biodegradable Fibres based on Poly (lactic acid) PLA
Biodegradable fibres produced from inherently biodegradable polymers. Biodegradable polymers breakdown in
physiological environments by macromolecular chain scission into smaller fragments, and ultimately into simple
stable end-products The degradation may be due to aerobic or anaerobic microorganisms, or biologically active
processes (e.g. enzyme reactions) or passive hydrolytic cleavage. The degradation may be limited to the ends of
polymer chain or may take place at random points along the polymer chain resulting in chain scission. On
complete degradation, the fibre is broken down into monomer units or parts thereof. Degradable polyesters are
derived from four monomers, lactide, glycolide, butyric acid and caprolactone. They are characterized by
degradation times ranging from days to years, depending on formulation and initial molecular weight. These
biodegradable polymers are ecofriendly and biodegradable fibres find applications in medical textiles, biomedical
implants, sutures, meshes and drug release systems
Polylactic acid (PLA) is one of the most promising biodegradable polymer, PLA provides a unique combination of
advantages in that it is a material from annually renewable resources with the look and feel of other natural
fibres, yet with the performance properties of synthetic fibres.Some of the applications of fibre grade PLA are
resorbable sutures, implants for orthopaedics, surgical materials, thermoforms, injection-molded or blow-molded
containers, oriented and blown films, and nonwovens. The most interesting aspect of the polymer is that the
material undergoes hydrolysis of the ester linkage in the main chain during in vivo condition and leads to the
formation of nontoxic lactic acid, which is subsequently consumed in the carbohydrate metabolism in the human
body. It is the L-lactic acid which provides polymer with high mechanical strength and thus has an edge over the
D-form.
The trade names for some commercial PLA polymer are:
Lacty_ from Shimadzu Corp.,
Lacea_ from Mitsui Chemicals,
EcoPLA_ from Cargill Dow.
A flow diagram summarizing the product cycle for poly(lactic acid) is shown in Figure 1.
Figure 1: Product cycle of Poly(lactic acid)
The process for manufacturing of PLA comprises of two main steps.
1. The first stage involves production of lactic acid monomer from the starch and
2. The second stage concerns the conversion of lactic acid monomer to polylactic acid.
Monomers for Synthesis of Poly (lactic acid)
Polylactic acid synthesis is possible in two ways, the polycondensation of lactic acid and the ring-opening
polymerisation of lactide. In both the cases lactic acid is the starting monomer. The lactic acid exists in two
configurationsL-lactic acid which is optically active and polarizes light to right (denoted by- or d), and D-
configuration polarizes light to the left (denoted by+ or l).

Figure 2. Stereoisomers
of lactic acid
Dimerization of these lactic acids to a six membered lactides as shown in Figure 3.

Figure 3. Dimeric lactide


isomers
An equimolar mixture of the two lactides is optically inactive. Therefore, the purity of the monomers can be
estimated by measuring their optical activity.
Poly lactic acid synthesis

Direct polycondensation

Direct polycondensation results in low molecular weight prepolymer (M 2000-10000). Therefore,it can react with
w

isocyantes, epoxides or peroxide to produce a range of molecular weights. Alternatively, azeotropic dehydrative
condensation can be used to obtain high molecular weight PLA.
Ring opening polymerization or by lactide
Poly(D-lactic acid) (i.e. PDLA) and poly(L-lactic acid) (i.e. PLLA) can be polymerized by ring opening
polymerization of D(+)-lactide and L(-)-lactide, respectively (Figure 4). Ring opening polymerization can be
performed in bulk at 140190 C for 1012 h under reduced pressure, in the presence of catalyst. The
polymerization conditions are the same for D(+) and L(-) lactides and the resulting polymers can be purified by
repeated precipitation using dichloromethane as solvent and methanol as the precipitant.

Figure 4. Lactide formation and polymerization of lactic acid

Figure 5. Ring opening


polymerization of lactides
Direct preparation from racemic monomer with racemic catalyst
The polymerization of a rac-lactide using a normal catalyst like Sn(octoate) results in an amorphous polymer
2

due to random placement of D- and L- lactide units in the individual PLA chains. These limitations can be
eliminated if stereoselective polymerization of racemic lactide is carried out using a racemic catalyst as shown in
Figure 6.

Figure 6. Stereoselective
polymerization of racemic
monomer with racemic
catalyst
The catalyst is a mixture of (+) and (-) complexes of a chiral schiff base with aluminum. The (+) catalyst
meditates polymerization of only the L-lactide in the mixture. The (-) catalyst similarly polymerizes the D-lactide.
Although the formed polymer is a mixture of all D and all L-chains, the isotactic chains co-crystallize to form a
stereocomplex that imparts a high degree of crystallinity to the material.This technique yields nearly
monodisperse chains (M /M = 1.05) consistent with a living polymerization and the absence of
w n

transesterification.
High M PLA prepared from PLLA, are partially crystalline with a T of 175-180 C, T of 60 C, crystallization
w m g

temperature (T ) of 100-105 C, and a decomposition temperature (T ) of 185-190 C. It is brittle and undergoes


c d

unzipping to lactide when thermally processed. Copolymerisation with D-lactic acid and other hydroxyacids to
obtain polyesters with a lower T and thus better thermal processing characteristics has been the common
m

approach to obtain useful PLA. Stereo copolymers of L-lactic acid and D-lactic acid have lower crystallinity and Tm

than the homopolymer of L-lactic acid and the polyester properties vary with the optical purity with the 50/50 DL
polylactic acid (PDLLA) having no crystallinity at all. Variation of the optical purity is the most commonly used
means to produce PLA of different properties.
PLA Fibre Spinning and Properties
PLA Spinning
PLA can be converted to fibres using all the techniques suitable for synthetic fibres. PLA can be processed on the
conventional fibre spinning and downstream textile fabrication equipment and have processing advantages. The
solution spinning techniques have been effective in controlling the degradation due to relatively lower processing
temperatures, thereby providing better tensile properties of the fibre.
Melt spinning
PLLA with a viscosity average molecular weight (M ) around 0.53.5 x 105 is used for melt spinning. PLLA fibres
v

are produced by first melt extrusion, and then hot drawing. The melt-extrusion is normally carried out above the
melting point in the temperature range of 185 to 240 C through a spinneret with L/D ratio in the range of 210.
Lower extrusion temperatures are used for polymers produced from monomers with lower optical purity. Before
melt-extrusion, the polymer is dried at 120 C under vacuum for 316 h to lower the moisture content of the
polymer to 0.005 wt%. This is necessary to minimize hydrolytic degradation of the polymer during spinning.
Poly(L-lactic acid) filaments can be spun at high speed take-up velocities of up to 5000 m/min. The crystallinity,
birefringence, tensile strength, Youngs modulus and yield strength, all exhibit maxima at take-up velocities
between 3000 and 4000 m/min. The boiling water shrinkage exhibits a minimum in this range. This implies that
a stable morphology is developed through stress induced crystallization at this speed. The maximum tensile
strength of the as-spun filaments has been reported to be 385 MPa and the maximum modulus to be 6 GPa.
Very low speed melt spinning produces fibres which are essentially amorphous and can be drawn up to 10 times
to form mechanically strong fibres with tensile strength of 870 MPa and modulus of 9.2 GPa.
In a second step, the drawing of as-spun fibres is carried out in air at temperatures from 80 C up to 160 C
with a hot plate drawing apparatus to improve the mechanical properties. Heat setting can also be carried out in
dry air at 80 C to 160 C for 10 min.
All PLLA fibres produced by melt spinning show a considerable reduction of viscometric molecular weight. The
molecular weight degradation is attributed to the ester group cleavage as a consequence of the hydrolytic
process at the high temperature of melt spinning in the presence of residual water in the polymer. The molecular
weight degradation during spinning can be reduced by use of solution spinning process.
Solution Spinning
Solution of PLLA may be wet or dry spun. The wet spinning can be carried out by extruding solutions of PLLA
prepared in chloroform into a coagulation bath containing toluene at 110 C.

Figure 8. Wet spinning


apparatus
The concentrations used are in the range of 612 wt% depending on the molecular weight (in the range 3-5x10 5)
of the polymer used. Molecular weights lower than 3X105 are unsuitable for wet spinning due to low solution
viscosity at extrusion temperature. After spinning, the fibres are dried. Low spinning speeds of about 2535
cm/min at the laboratory scale are reported to give fibres with no orientation. Dry-jet wet spinning technique can
also be used.
PLLA has also been produced by dry spinning. In this process, the heated polymer solution in chloroform is
extruded into a heated air chamber, where the solvent evaporates to produce PLLA filaments.

Figure 9. Dry spinning set-up


Solution dry-spinning of fibres, using binary solvent mixtures of chloroform (good solvent) and toluene (poor
solvent) lead to filaments with improved tensile properties. The fibres spun from chloroform/toluene mixture
have a porous texture. This is attributed to a more rapid phase separation in the presence of toluene, which is a
poor solvent. Such PLLA fibres are found to have high initial crystallinity and good drawability. The spinning
solutions are prepared by dissolving PLLA in chloroform and subsequently adding toluene.
PLA Fibre Properties
PLA is the only melt-processable fibre from annually renewable natural resources. It has a number of
characteristics that are similar to many other thermoplastic fibres, such as controlled crimp, smooth surface and
low moisture regain. Some properties of PLLA in comparison to PET are summarized in Table 1.
Table 1. Comparison of some properties between PLLA and PET
Density (g Refractive Moisture Smoke generation LOI
Fibre Flammability
cm )
-3
index regain (%) (m kg )
2 -1
(%)
Continues to burn for two
PLLA 1.25 1.35-1.45 0.4-0.6 63 26
minutes after flame removal
Continues to burn for six
PET 1.39 1.54 0.4 394 22
minutes after flame removal
PLA with a glass transition temperature (T ) between 5565 C is a stiff polymer at room temperature. The
g

melting temperature (T ) of PLA containing either the L- or D-isomeric form alone, is between 160170 C. This
m

low melting point compared to PET underlines one of the main restrictions for PLA in developing suitable
applications. Interestingly, the properties of PLA can be modified by adjusting the ratio and the distribution of the
D- and L-isomers in the polymer chain, and melting points as low as 130 C and as high as 220 C can be
obtained. This polymer has significant commercial potential as a textile fibre. Its mechanical properties are
considered to be broadly similar to those of conventional PET.
The tensile properties of PLA fibre as used in staple form for textile processing are shown in Figure 10. They are
very different from those of high tenacity polyester and more akin to wool with a high fibre extension when
stressed and relatively low final tenacity. The initial modulus (at 2% extension) is very similar to many other
textile fibres, but the yield point is very marked, the fibres (and spun yarns) stretches very easily once past this
point. A consequence, however, of the high elongation is that the work of rupture is relatively high giving yarns
and fabrics an acceptable performance in commercial use.

Figure 10. Tenacity- extension curves for PLA and other common textie
fibres (20 C, 65% RH)
The tenacity at break (3236 cN tex-1) is higher than for natural fibres although, of course, it can be varied
according to the degree of drawing that is applied to the undrawn yarn. It is relatively unaffected by changes in
humidity at ambient temperature, though as with other manufactured fibres there is a small but measurable
increase in elongation. As the temperature is increased the tenacity does reduce quite quickly with a concomitant
increase in fibre extension, a feature commonly found in synthetic fibres.
PLA is not a non-flammable polymer, however the fibre has good self-extinguishing characteristics as shown in
Table 1.
Medical Applications
The fibres based on these polymers can be used to make scaffold to culture and grow living cells. PLA and PGA
are the major bioresorbable fibres used in implants. They can either be used as a single polymer or by blending
a copolymer of PLA and PGA. Varying the proportions of PLA and PGA alters the degradation rate and strength
retention time of the fibre. These properties can be tuned depending upon to the requirements of specific
medical applications. During the process of degradation, fibrous connective tissues replace the degrading
implant. The key advantage of using these polymers is that no further surgery is required to remove the
products since they slowly degrade in the body without any side effects. Also, PLA-based materials have been
used for bone support splints.
MODULE 6. FIBRES FOR MEDICAL APPLICATIONS
6.2 Absorbent Fibres (2 lectures)
Absorbent Fibres
Absorbent fibres can be produced by two routes:
1. Modification of existing fibres or polymers
2. Using superabsorbent polymers
The first category of absorbent fibres is produced by hydrophilic modification or incorporation of hydrophilic
polymers in the existing fibre forming polymers. Highly water absorbent fibres are generally produced by using
the second approach i.e. using superabsorbent polymers. In this module, we will be dealing with the
developments in superabsorbent polymers used to produce highly absorbent fibres/fibrous products.
What are Superabsorbents?
Super Absorbent Polymers (SAP) are polymers that can absorb and retain extremely large amounts of a
liquid relative to their own mass. To further define the characteristics, a superabsorbent must remain insoluble in
the fluid it absorbs and the fluid absorbed by the material be strongly retained. Exertion of pressure must not
cause the fluid to move out. So, it is cross-linked to make it insoluble in the liquid it absorbs.

Figure 1. Superabsorbent
Polymers
Superabsorbent polymers are expanding into many product areas, e.g. agriculture, moisture barriers, sealants,
air-fresheners, toys, etc. Personal hygiene products & medical products, however, use more than 95% of the
total production of super absorbent polymers. The principal use is in disposable diapers and adult incontinence
products. Besides these, superabsorbent polymers have been used for newer applications like: preparation of
artificial snow, in gel actuators used as artificial muscles in robots for locomotion.
Initially superabsorbents were made either from chemical substitution on cellulose or by grafting polyelectrolytes
onto starch or cellulose and had good water absorption capacity. The superabsorbent polymers that are currently
being produced commercially are made of partially neutralized acrylic acid or sodium polyacrylate. Table 1
details a list of some commercial products available.
Table 1. World Wide Production of Superabsorbents
Producer Product name Composition Product form
Stockhousen ACRYSORB Polyacrylate Powder
Chemdal ARIDAL Polyacrylate Powder
Dow Chemical DRYTECH Polyacrylate Powder
Hoechst AG LAQUASORB Polyacrylate Powder
Allied Colloids ALSORB Polyacrylate Powder
BASF OASIS Polyacrylate Fibre
Sanyo SANWET Starch grafted Powder
acrylate/Polyacrylate
Sumitomo Seika AQUAKIP Polyacrylate Powder
Nippon
AQUARIQUE Polyacrylate Granular
Shokubai
The swelling and the elasticity of these polymers depend on the precise structure of the polymer network and
primarily on the cross-link density. The absorption properties of one typical superabsorbent OASIS are given in
Table 2.
Table 2 Properties of crosslinked acrylic acid copolymers OASIS
Property Water (g/g) Saline(g/g)
Free swelling 80 40
Absorption under
45 23
load
Mechanism of Absorption
The primary mechanism of liquid absorption is molecular diffusion of water into the particles coupled with
relaxation of the polymer chains. The driving force for the water to move inside the polymer, formed due to the
ionisation of neutralized acrylic acid. The initial diffusion of water inside the hydrophilic polymer causes ionization
of the neutralized acrylate groups into negative carboxylate ions and positive sodium ions. The negative
electrical charges along the polymer backbone cause mutual repulsion of carboxylate ions and also increase the
osmotic pressure inside the gel. This in turn results in expansion and swelling of the polymer chains due to
associated water. Finally, the crosslinks between the chains prevent the solubilisation of polymer in water and
also control the extent of swelling or absorption by restricting infinite swelling (Figure 2).

Figure 2. Mechanism of
absorption of water in
superabsorbent
Preparation of Superabsorbent Polymers
Superabsorbents are prepared by free-radical initiated polymerization of partially neutralized acrylic acid and/or
other comonomers e.g. methacrylic acid, along with a suitable cross-linker. The significant factors in these
processes are the monomer and the cross-linker concentrations, the initiator type and concentrations,
polymerization modifiers, the relative reactivity of the monomers, the basic polymerization kinetics and the
reaction temperature.
These are generally polymerized by one of the following techniques
Bulk Polymerization
Bulk polymerization is the simplest technique which involves only monomer and monomer-soluble initiators. High
rate of polymerization and degree of polymerization occur because of the high concentration of monomer.
However, the viscosity of reaction increases markedly with the conversion which generates the heat during
polymerization. These problems can be avoided by controlling the reaction at low conversions. The advantage of
bulk polymerization is that it produces high molecular weight polymer with high purity.
Solution Polymerization
In solution co-polymerization reactions, the ionic or neutral monomers are mixed with the multifunctional cross-
linking agent. The polymerization is initiated thermally, by UV-irradiation, or by a redox initiator system. The
presence of solvent serving as a heat sink is the major advantage of the solution polymerization over the bulk
polymerization. The prepared SAPs need to be washed with distilled water to remove the unreacted monomers,
oligomers, cross-linking agent, the initiator, the soluble and extractable polymer, and other impurities. This
technique is associated with the difficulty associated to drying and grinding of superabsorbent gel into smaller
particles.
Inverse Suspension Polymerization
In inverse suspension polymerization, the monomer solution is dispersed in the non-solvent forming fine
monomer droplets, which are stabilized by the addition of stabilizer. This polymerization method results in
spherical SAP micro-particles with size range of 1 m to 1 mm. The polymerization is initiated by radicals from
thermal decomposition of an initiator. The newly formed micro-particles are then washed to remove unreacted
monomers, cross-linking agent, and initiator. The technique has gained importance because of it allows easy
removal of water and isolation of product.
Crosslinkers
Generally polyelectrolytes are water soluble and they are easily rendered water-insoluble by crosslinking,
forming a chemical bridge between polymer chains. The chains are cross-linked during polymerization by
including a bifunctional monomer, a compound with two independent, polymerizable alkene functionalities. As
shown in Figure 3, one end of the crosslinking agent acts as a monomer in the polymerization of one chain,
while the other end of the crosslinking agent acts as a monomer in the polymerization of another chain. As a
result, the two chains are linked together.
Figure 3. Scheme for Co-
polymerization
Relatively small amounts of crosslinkers play a major role in modifying the properties of super absorbent
polymers. In addition to modifying the swelling and mechanical properties, the crosslinker affects the amount of
soluble polymer formed during the polymerization. Typical crosslinkers used are N,N- methylene
bisacrylamide,di- & tri-acrylate esters e.g. 1,1,1-trimethylol-propane triacrylate or ethylene glycol diacrylate. The
tendency of a cross-linker to be attached to the growing polymer chain depends on its relative reactivity ratio
with acrylic acid or sodium acrylate, etc. The choice of the cross-linker depends on the method used for
polymerization.

Figure 4. Chemical
structure of typical
crosslinkers used for
superabsorbents
Important Properties of Superabsorbents
The key properties of super absorbent polymers are:
a) Swelling capacity
b) And the elastic modulus of the swollen cross-linked gel.
Both these properties are related to the cross-link density of the network, the modulus increases and swelling
capacity decreases with increasing crosslink density. The swelling capacity or absorption also increases with
increase in degree of neutralization of carboxylic acid groups.
Figure 5. Change in
swelling capacity with
increase in a) Crosslinker
concentration, b) Degree
of neutralization.
The crosslink density of super absorbent polymers used in personal care applications is very low, about 0.03
moles of cross-linker per litre of dry polymer. Because of this very low concentration, the conventional
spectroscopic technique, such as IR spectroscopy & NMR are not very useful for characterizing the crosslink
density. Mostly the gravimetric methods are used to measure the swelling capacity, and rheological methods are
used to measure the modulus. The crosslink density can be estimated from these measurements by applying an
appropriate mathematical model of the relationship between network structures & properties.
Swelling Capacity or Free Swelling
The amount of liquid absorbed by 1 gm of the polymer is called the swelling capacity. The absorption of a liquid
by a polymer depends both on the nature of the liquid and the polymer. The swelling capacity depends on the
number of ionic units in the polymer, and the cross-link density.
The swelling capacity is calculated from the increase in mass of the polymer sample and is typically reported as a
ratio of the grams of fluid absorbed per gm of dry polymer. For personal hygiene applications, water and saline
absorption values are characterized.
Elastic Modulus
The elastic moduli of swollen gels are typically measured on a compact mass of swollen particles by means of an
oscillatory stress rheometer. The swollen mass of particles is packed into space between the plates of the
rheometer, and an oscillating shear stress is applied to one plate. The motion of the opposite plate of the
rheometer is measured and is related to the damping of the mechanical wave passing through the sample. The
shear modulus is calculated from the measurements.
Absorption Rate
The rate of absorption of a liquid by a polymer depends on the maximum amount of liquid that can be absorbed
as it provides the driving force for the swelling process. Lower crosslink density provides for larger maximum
swelling capacity and thus increased driving force. Other factors affecting the absorption rate are the particle
size and the particle size distribution in the sample, the density of the polymer and the specific surface area of
the particles. Small particle size and a high surface-to-volume ratio of the particles are necessary to increase the
overall absorption rate.
Absorbency Under Load
The use of super absorbent polymers in items of personal hygiene makes it necessary for it to hold the absorbed
fluid even under the action of applied pressure. This property is known as the absorption under load. Diapers
must absorb liquids under compressive loads of the order of 2.0 kPa, higher absorbency under load is desirable.
This is a composite property of super absorbent polymers, incorporating aspects of swelling capacities while
under a compressive stress, gel rigidity and flow of liquid through a collection of particles.
The measurement is made on a small sample of particulate super absorbent polymer that is confined in a
cylindrical test cell between a screen and weighted piston. The liquid contacts the polymer through the screen at
the bottom of the test cell, and is absorbed by the polymer until the gel particles become soft enough to collapse
into the free space surrounding them. This point is analogous to gel-blocking. When this point is reached the
sample effectively ceases to absorb any more liquid. The gel is then taken out centrifuged and weighed to find
the liquid retention capacity.
Polymers with higher elastic modulus resist the compression better than those with lower modulus and therefore
have higher absorbency under load.
Soluble Fraction
The soluble fraction is that part of the polymer particle that is not attached directly to the network. The amount
of soluble polymer is increased at lower crosslink density and at lower crosslinker efficiency (which occurs at high
conversion of monomer) and depends on the relative relativities of the cross-linker and the acrylic acid.
The uncrosslinked chains do not contribute to the modulus of the sample, but can be solvated and contribute to
swelling if they are retained in the gel phase. The presence of soluble polymer in the gel lowers the chemical
potential of the water in the gel, thereby increasing the difference in the chemical potential of water between the
phases, which is the driving force for swelling. Because of an increased driving force for swelling, the swelling
rate can be increased by the presence of soluble polymer in the gel. However, once extracted from the gel, the
soluble polymer can depress the swelling of the sample by reducing the chemical potential of water in the
external liquid phase.
Approaches to Improve Properties of Superabsorbents
As discussed above, ideal superabsorbent polymers should have high absorption capacity. However, a
complicating factor enters the picture with high-swelling, small particles of superabsorbent polymers. The
collection of small particles can exhibit a phenomenon called gel-blocking. The surfaces of the particles swell
rapidly due to large driving force and small diameter. The surface layers of neighbouring particles quickly become
soft and sticky owing to the inevitable presence of some soluble polymer in the particle. The individual polymer
networks may entangle with each other forming large-sized agglomerates of partially swollen gel. A dramatic
reduction in the absorption rate is then observed due to the molecular diffusion-limited transport coupled with
the large particle size. This can be overcome by improving the gel strength without compromising the swelling
capacity. This has been overcome by surface cross-linking of the polymer.
Surface Cross-linking
As mentioned earlier, in conventional super absorbent polymers, a complicating factor enters the picture due to
the high swelling but small particle size of the polymer. This is known as gel-blocking.
To avoid gel-blocking, the surface of super absorbent polymers can be further modified by using another cross-
linking agent, so that there is a higher degree of crosslinking on the surface of the polymer than in the core.
Super absorbent polymers thus produced have higher mechanical properties while maintaining high absorption
properties, as the fluid does not saturate the surface and prevent further penetration of the fluid to the core.

Figure 6. Superabsorbent
structure with high
swelling capacity and gel
strength
Among the cross-linking agents that have been used to surface crosslink prepolymerized polyacrylic acid are
ethylene glycol diglycidyl ether and ethylene carbonate. Other means such as spraying methanol solution
containing 0.1-20% w/w of a poly quaternary amine or plain heat after-treatment has also been used to achieve
surface crosslinking and the performance characteristics were significantly improved.
Delayed Swelling
Another method developed to improve the performance of super absorbent polymers is delayed swelling.
Delayed swelling enables better penetration and alleviates gel blockages. This comprises of a polyelectrolyte
hydrogel irreversibly crosslinked with a polyvalent metal cation having a valence of at least two.
Osmotic Agents
The presence of osmotic agents such as urea, sucrose, etc. in the core of super absorbent polymers increases
both the equilibrium water absorption and the water absorption rate. This is achieved in an absorbent structure,
which comprises a super absorbent material, which defines a chamber, containing an amount of an osmotic
material. The chamber is desirably substantially completely surrounded and encapsulated by the super absorbent
material. Due to the osmotic material present within the chambers, liquid is drawn through the water-swollen
super absorbent material, which liquid then fills the chamber. As the chamber expands, more and more liquid
can be drawn through the super absorbent material into the chamber until equilibrium is reached. Thus, the
absorptive capacity per gram of super absorbent material is increased.
In another aspect, the presence of osmotic material within the chamber causes the super absorbent material to
absorb liquid at a more rapid rate, the osmotic driving force being higher.
Shape Control
The physical form of superabsorbents in the fibrous form also enhances the absorption properties. This is due to
the small diameter of the fibres, which gives a very high surface area for contact with the liquid. Also the fibre
surface is not smooth. It has a crenulated structure with longitudinal grooves. These are beneficial in
transporting moisture to the surface. Typically the fibre will absorb 95% of its ultimate capacity in 15 seconds. It
is possible to process superabsorbents in blends with other fibres on most of the conventional nonwoven
processing routes to produce fabrics suitable for medical products such as disposable incontinence products,
wipes and absorbent pads, drapes, ostomy bags, and in wound care.

Copyright IIT Delhi 2009-2011. All rights reserved.

MODULE 7. SMART, FUNCTIONAL & SPECIALITY FIBRES


7.1 Environmentally Responsive (Smart) Textiles ( 4 Lectures)
Introduction to Smart Textiles
What are Smart Textiles?
Conventional textiles are used to cover the human body and function as a protective layer for the body from
dust, sunlight, wind, and other contaminants present in the normal living environment. It is also used for
carrying out technical functions which utilize their flexible and strong structure. The textiles may be used
for additional function specific to an adverse or extreme climate, job-environment or profession to
enhance adaptability and/or productivity of the user. When textile assumes an additional function over and above
the conventional purpose as mentioned above, it may be regarded as Smart Textile. And if this additional
functionality changes with change in use conditions, then textile may be regarded as Active Smart or
Intelligent Textile.
Mother Nature is the main source of inspiration for such innovations. Human skin is an excellent example of
smart textile with functional capabilities which can perform protection, sensing and actuation. Some other
examples seen in nature are - Chameleons change colour according to the environmental situation, leaves
of Mimosa pudica collapse suddenly when touched, sunflower turn towards the Sun.
By understanding the natures design concepts, researchers are trying to bridge the disparity and gap between
synthetic and natural materials.
The mechanism of functionality expected in smart textile can be understood from Figure 1.

Figure 1. Mechanism of Smart Textiles


Smart Textile or Responsive Textile can be broadly classified based on the active responses exhibited by them:
Change of Shape
o Reversible or one way
o Increase or decrease of dimensions, bending etc.
Storage and release
o Heat
o Drugs, chemicals etc.
Electronic functionality
o Communication, entertainment, monitoring
In this chapter we would learn about A). Shape changing fibres and B). Thermo-regulated (heat storage and
release) textiles

Shape changing Textiles (fibres, yarns and fabrics)


Shape changing fibres, yarns and fabrics are developed using stimuli sensitive polymers (SSPs). These polymers
show a reversible transformation from one state to another as a response to various stimuli from the
environment. These polymers are also known as smart-polymers or intelligent-polymers. Across the transition
temperature, the linear SSPs change from soluble (clear) to insoluble form (turbid). However, in the gel form
they swell and deswell because of the presence of cross-links by absorbing or releasing water. For most
applications these are generally used in the gel or cross-linked form. The change may occur in their
configuration, dimension or physical properties with a small change in appropriate stimuli.
Figure 2. Smart breathable textiles using temperature sensitive polymers
Among the various stimuli-sensitive polymers, the temperature-sensitive polymers are the most widely studied
polymers. Besides the temperature stimulus, the other chemical and physical stimuli which bring about a
reversible transition in such polymers include electric field, solvent composition, light, pressure, sound, stress,
magnetic field, and chemical and bio-chemical stimuli (i.e. pH and ions). These polymers provide a big
opportunity for creating intelligent materials.

Figure 3. Schematic representation of different types of stimuli


Smart or intelligent materials that respond to their environment by changing their shape or properties are useful
for various critical applications in biomedical and engineering fields such as controlled drug delivery, separation,
enzyme-activity control, tissue culture and now recently for artificial muscles and smart textiles.
Figure 4. Application areas for Smart Polymers
As these hydrogels are mostly synthesized using crosslinkers (like - N,N' - methylenebisacrylamide or ethylene
glycol dimethacrylate) during polymerization, this cross-linked physical structure results in a number of
drawbacks
The stimuli-sensitive polymer-gel structures are weak /have poor mechanical properties and therefore are
required to be used as thick structures. However, in thick gel structures, the transitional response is poor due to
slow diffusion.
The simplest way to improve the response time is to make hydrogels thinner, smaller and stronger.
The processing of these materials into thin shapes and their stabilization or integration to textile materials is
likely to solve result in strong structures, which can be used in thinner dimensions and would show higher
magnitude of response in short span of time. Such responsive textile structures would show enhanced
performance compared to gel structures.
Smart or intelligent textile structures can be developed using the following approach:
Step 1. Preparation of suitable linear polymers with tuned response behaviour
Step 2. Shaping these linear polymers into desired thin structures (by solution spinning or coating)
Step 3. Stabilization of shape by cross-linking (chemical or physical)
Some of the approaches that are used for imparting smart functionality to textile are shown in Figure 5.
Figure 5. Schematic representation of different approaches used for imparting smart functionality
By appropriate selection of responsive polymer containing reactive functional groups for integration
or stabilization, shape changing textile structures with very fast response can be developed for
various applications. In the next lecture we would study about temperature responsive textiles.

Temperature Responsive Textiles


Temperature responsive textiles are developed using temperature sensitive polymers (TSPs). These polymers
exhibit transition known as Lower Critical Solution Temperature (LCST).These polymers have both hydrophilic
and hydrophobic groups in their structure.
TSPs present a fine hydrophobic-hydrophilic balance in their structure, and small temperature changes around
the critical temperature, makes the chains to collapse or to expand responding to the new adjustments of the
hydrophobic and hydrophilic interactions between the polymeric chains and the aqueous media.
Some examples of TSPs and their transition temperature are shown in the Table 1
Table 1. List of Temperature Sensitive Polymers with their LCSTs
Class Polymer Name/Chemical repeat unit LCST,C
poly N isopropyl
32
acrylamide(PNIPAm)
poly (N-alkyl substituted poly(N-n-propylacrylamide) 16-19
acrylamides)
poly(N-isopropylmethacrylamide) 40
poly(N-cyclopropylacrylamide) 4-6
poly (N-vinylalkylamides) poly(N-vinylcaprolactam) 32-35
Poly-N-isopropyl acrylamide (PNIPAm) is the most widely studied thermo-responsive polymer. It has hydrophobic
backbone and a pendant group which has a hydrophilic amide moiety and a hydrophobic isopropyl moiety.

Figure 6. Hydrophilic and hydrophobic moieties in PNIPAm polymer(Transition temp. 32 C)


Below LCST, the hydrophilic interactions (the hydrogen bonds formed between water molecules and N-H or C=O
groups of PNIPAm) dominate and polymer becomes soluble in water, while above this temperature hydrophobic
interactions dominate and polymer becomes insoluble in water.
The transition temperature of these TSPs can be tuned by changing the ratio of hydrophilic and hydrophobic
groups, incorporation of additives, or by changing the nature of polymer system. As mentioned above the
polymer gels prepared from these thermo responsive monomers change shape by swelling in water below
transition temperature and deswell above transition temperature.
As explained before, the response of these materials can be enhanced by processing a suitably designed TSP into
structurally strong thin films, fibres, coatings, and chemically integrated TSP with yarns and fabrics using the
three steps. Using a copolymer based on N-tert butylacrylamide and acrylamide, temperature responsive smart
textiles have been reported. The chemical structure of the temperature responsive copolymer and the chemical
reaction showing its integration with textile are shown below. Here, N-tert butylacrylamide is a responsive
monomer and acrylamide is a reactive monomer for attachment or cross-linking reaction in presence of suitable
cross-linkers.

a)

b)
Figure 7. a) Preparation of temperature responsive polymer, b) Integration of polymer with substrate
The TSP synthesized in conventional gel forms could be cut with difficulty into 2 mm thick discs. This gel disc
showed a swelling of 490%, and took 90 minutes to attain 70% swelling, while the deswelling took 50 minutes.
Shape Changing Fabric
Shape changing model fabric prepared by using cotton yarns coated with temperature responsive polymer and
subsequent cross-linking. The cross-links (i.e., covalent bonding) were formed using polycarboxylic acid between
amide side-groups of the copolymer and hydroxyl-group of the cellulosic substrate (in case of coatings).

The transition properties and the response time of the TSP in the different processed forms in comparison to
polymer-gel discs are given in Table 2.
The responsive coated yarn shows very high degree of swelling and deswelling across the transition temperature
in a very short span of time. For 70% of equilibrium swelling, it takes 3 minutes compared to 90 minutes for
gels.

Table 2.Comparison of transition properties of TSPs in different processed forms

Swelling Time for


70% of Time for complete
Sample type Thickness (change
in shape equilibrium deswelling
%) swelling
Gel disc
2 mm 490 90 min 50 min
(conventional)
Coated on Yarn 39 m 4500 3 min 10 sec
Fibre 30 m 17800 <5 sec <1 sec
The optical photographs of the model fabric at different temperatures are shown in Figure 8. At temperatures
lower than transition temperature the yarns are highly swollen, while above the transition temperature, the
yarns deswell by releasing all the water. The percentage cover of the model fabric (immersed in a water bath)
changed from 0% at 6 C, to 39% at 30 C, and 57% at 80 C. The change was completely reversible for
several cycles. The change in the porosity (percentage cover) with temperature can be clearly seen in optical
microphotographs given in Figure 8.

Figure 8. a) Optical micrographs of model fabric at different temperature


b) Corresponding percentage cover of model fabric at different temperatures
Shape Changing Fibres
The TSP was also successfully converted into a shape changing textile fibre of fine diameter. The fibre underwent
change in both diameter and length with change in temperature as shown in the optical micrographs (178 %
change in volume ) Figure 9.
Figure 9: The optical micrograph of thermo-responsive shape changing fibre at 100 X (i) Deswollen
fibre in water at 80 C (ii) Swollen fibre in water at 6 C.
The time for 70% transition (swelling) was found to reduce dramatically from 90 minutes for the 2 mm gel disc
to less than 5 seconds for the TSP fibre, while the change in shape (swelling ratio) of the fibres increased by 36
times (shown in Table 2 ).
The rate and extent of swelling (equilibrium swelling) can be tuned by varying the degree of cross-linking on rate
of transition and equilibrium swelling of the fibre is shown in the Figure 10.

Figure 10. Rate of transition of shape changing fibres at two different crosslinking levels (a) lower
and (b) higher

Figure 11. Reversibility & cyclability of SSP coated fabric immersed in water at two different
crosslinking levels (a) lower and (b) higher
pH-Responsive Textiles
What are pH responsive polymers?
Polymers that can sense the pH of their environment as a signal, judge the magnitude of the signal and change
their properties accordingly are known as pH responsive hydrogels. In this case, the key element of the system
is the presence of ionizable weak acidic or basic moieties attached to a hydrophobic backbone. The functional
groups include ionisable acidic pendant groups such as carboxylic and sulfonic acids or basic groups like amine
that can accept and donate protons in response to the environmental change in pH. As the environmental pH
changes, the degree of ionization in pendant groups undergo dramatic change at a specific pH called pK . This
a

rapid change in the net charge of pendant groups causes an alternation of the hydrodynamic volume of the
polymer chains. This results in a transition from collapsed hydrophobic state to soluble hydrophilic state of the
polymer.
Figure 12. Effect of pH on chemical structure a) Poly(acrylic acid), b) Poly (N,N diethylamino
ethylmethacrylate)
Some systems based on acidic carboxylic acid group co-monomers or basic amino group containing co-
monomers are shown in Table 3 . The hydrogel swelling and deswelling properties depend on several factors
including their hydrophobic- hydrophilic nature, crosslink density (elasticity), charge density and pK .a

Table 3. Commonly used synthetic monomers and polymers for pH sensitive hydrogel
Responsive
Monomer Responsive to
group
Acrylic Acid
-COOH
& its derivatives
Alkaline pH
Vinyl monomers with sulphonic
-SO H
acid
3

N-Vinyl pyrrolidone NH 2

Or Acidic pH
N,N`-diethyl amino ethyl
methacrylate Substituted
Amino
These hydrogels are an attractive alternative for artificial muscles. However, the limiting factor is the poor
mechanical properties, which are consequence of high water content of the hydrogels. Contrary to hydrogels,
polymeric fibres exhibit very good mechanical properties as a result of high degree of orientation and
crystallinity. Therefore for making artificial-muscles, sensors and actuators; thin fibre shapes with enhanced
transitional properties are desirable.
Copolymers of acrylonitrile and acrylic acid are expected to result in gel fibres with lateral organisation of
crystallites in oriented structure as well as pH sensitivity. Such fibres have been reported by two routes:
modification of commercial polyacrylonitrile fibre
copolymerization route
In first approach, shape changing gel fibres with a fine diameter were prepared from commercially available
polyacrylonitrile by preoxidation and subsequent saponification. During the preoxidation step some of the
pendant nitrile groups form crosslink, while in the subsequent hydrolysis step the uncrosslinked nitrile groups
can be converted to carboxamide and carboxylic acid groups.
Figure 13. Modification of Acrylic Fibre
Acrylic acid moieties provide the pH response while oxidized PAN regions provide the strength and structural
integrity. This approach results in mechanically strong pH sensitive gel fibres suitable for artificial muscle
applications.
These fibres show muscle-like expanding and contraction behaviour stimulated by pH change in the
environment. Strong alkaline solution (2N NaOH) and strong acidic solution (2N HCl), induced a more rapid
change in length. Equilibrium was achieved in about 1-2 seconds. Compared to swelling, the deswelling was still
faster and the entire change occurred spontaneously (<1 seconds). The fast transition obtained in these fibres is
due to the large surface to volume ratio provided by the fine fibre structure compared to hydrogels. The fibres
could be repeatedly subjected to cycles of elongation and contraction. The increase in length was found to be
about 55%.
As shown in Figure 14, excellent reversibility was obtained indicating the stability of structure. And the
transition is sharp. However, these fibres suffer with major drawbacks of being black (due to oxidation) in colour,
brittle, and high cost of production.

Figure 1 4. Cyclability behaviour of pH responsive fibre produced by modification of acrylic


In order to overcome the above drawbacks, another novel approach was to solution spin pH sensitive fibres from
a specially designed copolymer of acrylic acid and acrylonitrile (Figure 15). Unlike oxidized PAN fibres, these
fibres are white in colour, have high impact strength and show even higher response. The interesting feature of
the newly designed fibres is that it is not chemically crosslinked. Rather the physical structure of the fibre has
been tuned to give both responsiveness and structural stability.

These pH sensitive fibres exhibited increase in size at pH 10 in the range of ~1300% and decrease in size at pH
2 to near the original volume (range of 120-180 %) during the first two cycles; however in the subsequent
cycles the increase is about 3300 % while nearly same shape and size was obtained at lower pH. The increase in
the swelling ratio from the third cycle onwards could be due to opening-up of the structure. The response was
reversible and stable in subsequent cycles. The swelling deswelling behaviour has been shown in Figure 15 b.
Figure 1 5. a) Controlled Radical Co-polymerization, b) Swelling De-swelling cycles
Thermo-regulated textiles
Thermo-regulated textile can be also classified as an environmentally responsive textile. As the name suggests,
the thermo-regulated textile means textile that can help in regulating the body temperature. The most
comfortable skin temperature for human body is 33.4 C.
The human body itself regulates the body temperature by controlling the release of heat by blood vessel
dilatation or constriction, muscle and sweat gland activity etc.
To keep the skin temperature between 30.4 -36.4 C, we need to put on or take off clothings according to
external temperature. However, if clothing could automatically change its thermal resistance according to
temperature, it can control the speed of heat release and regulate the inner temperature.
The thermal comfort can be increased by use of certain materials known as Phase Change Materials (PCM).
PCMs are the materials which undergo a phase change from solid to liquid by absorbing certain amount of heat
and a phase change from liquid to solid by releasing certain amount of heat. Because these materials have to
exist as liquids in one of the transition states, they need to be encapsulated to protect them from leaking out of
the clothing during a phase change.
Phase Change Materials

Figure 16.Mechanism of PCM


Clothing with the encapsulated phase change materials (PCM) can help to retain a constant temperature buffer
and provide better comfort.
There are numerous situations where these can be beneficial and find applications. These include professions
where the person has to undergo extreme changes in immediate climate. For example pilots uniform in a fighter
plane, soldiers uniform in extreme climate zones, uniforms for workers working at extreme temperatures, fire
fighters, tents and temporary structures in extreme climates, automobiles, etc.
Phase change materials store energy when they change from solid to liquid and dissipate it when they change
back from liquid to solid. It would be most ideal, if the excess heat a person produces could be stored
intermediately somewhere in the clothing system and then, according to the requirement, activated again when
it starts to get chilly.

Figure 17. Schematic of Microcapsules


The key parameters of microencapsulated PCMs are particle size and uniformity, high core-to-shell ratio, thermal
and chemical stability, and resistance to mechanical action. Most early studies of latent heat storage focused on
the dehydration and hydration of inorganic salt hydrates due to their high energy storage density and high
thermal conductivity. However, inorganic salt hydrates are corrosive and are incompatible with several materials,
exhibit supercooling and phase separation during transition under thermal cycling. In an effort to avoid some of
the problems inherent in inorganic PCMs, the research interest had turned toward the characteristics of
numerous organic substances and their mixtures as novel PCMs, as well as the enhancement of heat capacity,
thermal stability, thermal conductivity and durability of the composites enclosing PCMs.
For clothing applications, the appropriate PCMs are the ones that exhibit phase transition in a temperature range
from 18 C to 35 C. Paraffin waxes, especially n-eicosane, n-octadecane and n hexadecane are mostly preferred
for textile applications due to their high latent heat and the phase change temperature interval. Characteristics
of PCMs, the composition of shell and the amount of microcapsules added into the structure are the main factors
that control the thermal management in the textile product. When a sufficient amount of micro PCM is added for
coating of fabrics, a suitable thermal management in the textile product, meeting the specified end-use need can
be provided.
These are encapsulated using two different methods:
In-situ polymerization and
Interfacial polymerization method.
Figure 18. Optical micrograph of the PCM capsules at the magnification of 500

Figure 19. Application of microcapsules to textiles.

Copyright IIT Delhi 2009-2011. All rights reserved.

MODULE 7. SMART/FUNCTIONAL SPECIALITY FIBRES


7.2 Non Circular /Profile fibres (1 Lecture)
Fibres with non-circular cross-section and hollow fibres
The cross-section or geometry of melt spun fibre essentially depends on the design of spinneret holes through
which the initial extrusion takes place. Synthetic fibres such as polyester and nylon are generally produced using
spinneret with circular holes and have a circular cross-section.While in the case of solution spinning and
coagulation process which involve mass transfer result in non-circular cross-section even when circular holes are
used.
Why fibres with non circular cross-section?
The natural fibres do not have a perfect circular shape, cotton has a bean shaped cross-section and silk has a
roughly triangular cross-section. Non-circular cross-sections are observed to result in greater lusture, high
covering power, improved handle, light-weight and warm preservation.The non circular cross-sections of these
fibres result in excellent capillarity and wicking properties for removing moisture, therefore are used for diapers,
sanitary towels,filter media,shoe liners and wound dressings. Therefore, filaments with non-circular cross-
sections are desirable for achieving these special effects.
Approaches for producing non-circular fibres:

The modified filament cross-sections result either by coalescence or fusion of melt streams below the spinneret
or directly from extrusion through profiles capillaries.
The major challenge for achieving non circular fibres is spinneret design and optimization of spinning parameters
for different polymers with unique rheological properties. The cross-sections of fibres and spinnerets used for
producing these are shown in Figure 1.

Figure 1. The cross-sections of fibres and its spinnerets


The reshaping of filament along the spinline depends primarily on the time of solidification,the longer this time
period, the greater the degree of reshaping. The factors that increase the possibility or extent of reshaping are:
Lowering of melt viscosity
Increase in spinning temperature
Lowering of throughput rate
Increase of spinning speed as it reduces the time available for solidification
Contour of spinneret
The structural and cross sectional shape can also be changed in high-speed melt spinning.
In general, the spinnerets orifices of diameter 0.18-0.45 mm and length 0.4-0.8 mm are used for producing
circular cross-sectional shape. For producing some other cross-sectional shapes typical dimensions and design of
spinnerets is given below.
Tilobal
The trilobal cross-section was the first departure from circular cross-section and was introduced by DuPont in
USA to produce lustorous yarn and fabric.The fibres can be produced using a typical spinneret orifice shown in
Figure 2.

Figure 2. Trilobal cross-section of fibre


Twin trilobal fibres resemble silk fibres and are very lustorous.These can be produced by conjugated
bicomponent spinning of trilobal cross-section yarn.The three tips of the trilobal crosssection may consist of
polymer that is easily soluble and results in special twin trilobal cross section ( Figure 3).
Figure 3. Twin trilobal cross-section
The rectangular shaped cross-section fibres are produced using rectangular spinnerets. A typical spinneret with
dimensions and the dimensions of the fibre produced using this are shown in Figure 4.

Figure 4. Spinneret for fibre with rectangular cross-section


For hollow fibre production, it is important to consider the die swell and the spinneret dimensions are designed
accordingly. A typical spinneret with dimensions and the resulting hollow fibre with dimensions is shown in
Figure 5.

Figure 5. Spinneret designs for hollow fibre and extruded hollow fibre
Other methods like separation of bicomponent fibre and thin-film splitting are also used. These are discussed in
the next chapter.
Copyright IIT Delhi 2009-2011. All rights reserved.

MODULE 7. SMART/FUNCTIONAL SPECIALITY FIBRES


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

Why Bicomponent Fibres?


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

Core-sheath

Side by side

Segmented pie or citrus fibres

Islands in the sea



In addition to these main classes, a wide variety of bicomponent fibres having different cross-sectional
geometries can be produced.
Typical Applications:
The bicomponent fibres can have a range of functionality and find applications for different end-uses as given in
Table 1.
Table 1. End-Use Applications of Bicomponent Fibres depending upon different functionalities
Functionailty Some End-use Applications
Antistatic Lining clothes,workwear,knitted fabrics,underwears
Liquid absorbing Sports wear,felt pens,liquid absorbers,underwears
Self-crimping Stockings,beddings,heat insulators,knitted fabrics,carpets
Thermal Bonding Nonwoven fabrics,beddings,mattresses, printing screens,cushions,
Electro-conductive Carpets,seatings,workwear,kinitted fabrics
Light-conductive Communication,decoration,telephone
Enhancement of properties such as - mechanical properties,
Other
aesthetics,dyeability,water repellency,flame retardancy

Spinning of Bicomponent Fibres


For proper spinning of two components it is required that:
Viscosities of the two polymer fluids are comparable. The viscosity should be high enough to prevent
turbulence after the spinneret
Drawability of the two polymers should also be comparable, otherwise splitting may occur
Compatibility of both components with the spinning method that is melt spinning or solution spinning is
also important
The first commercial bicomponent fibre was introduced by DuPont in the mid 1960s. This was a side-by-side
hosiery yarn called "cantrese" and was made from two nylon polymers, which, on retraction, formed a highly
coiled elastic fibre. In the 1970s, various bicomponent fibres began to be made in Asia, notably in Japan. Very
complex and expensive spin packs were used for manufacturing. These techniques were found to be technically
unsatisfactory and excessively expensive. Later in 1989, a novel approach was developed using thin flat plates
with holes and grooves to route the polymers. This process was very flexible and quite price effective.
These are melt-spun in a specially designed spinning manifold. Separate extruders and metering pumps are used
for both components. Ratio of the polymers can be controlled by varying the speed of the metering pumps.
Figure 1. Photograph of a Bicomponent Spinning Machine

Figure 2. Sketch showing parts of Bicomponent Spinning Machine


Core-Sheath Bicomponent Fibres

In core sheath structure, one of the components called core is fully surrounded by the second component known
as sheath. In this configuration, different polymers can be applied as a sheath over a solid core of another
polymer, thus resulting in variety of modified properties while maintaining the major fibre properties.
Figure 3. Different types of bicomponent fibres a)-d)Coresheath, e) Eccentric core-sheath and
f)Multiple core-sheath
Concentricity/eccentricity of the core can be tuned according to end application. If the product strength is the
major concern, concentric bicomponent fibres are used; if bulkiness is required at the expense of strength, the
eccentric type of the fibre is used.
These fibres can be useful for applications where
Core imparts strength (reinforcing material) and sheath has dyeability, soil resistance, heat-insulating,
and adhesion properties. Some examples include:
o bonding fibres used in carpets, upholstery etc., where the sheath is made of PE and core is made
of high melting point material like nylon.
o antisoil-antistatic fibres, made using a PET-PEG block copolymer containing polyester core
Sheath can be made from expensive material to increase visual appearance. And the core can be of low
cost material to control cost.
For making self crimping fibres. Crimp can be controlled by changing the eccentricity. Eccentricity of core
can be varied to balance strength and bulkiness: used in pillows and furniture.
In a simple technique to produce core sheath fibres, the two polymer liquids are separately led to a position very
close to the spinneret orifices and then extruded in a core sheath form as shown in Figure 4.

Figure 4. Technique for Core-Sheath Fibre formation


In case of concentric fibres the core polymer is in the centre of the spinning orifice outlet and flow of the core
polymer fluid is strictly controlled to maintain the concentricity of both components, while eccentric fibre
production is based on following approaches:

eccentric positioning of the inner polymer channel and controlling of the supply rates of the two
component polymers
introducing a stream of single component merging with concentric sheath-core component just before
emerging from the orifice
deformation of spun concentric fibre by passing it over a hot edge
coating of spun fibre by passing through another polymer solution
spinning of core polymer into a coagulation bath containing aqueous latex of another polymer
Side by Side Bicomponent Fibres
These fibres contain two components lying side-by-side. Both components are divided along the length into two
or more distinct regions. These are generally used to make self-crimping fibres due to different shrinkage
characteristics of the two components. In some applications, different melting temperatures of the fibres are
taken advantage of when fibres are used as bonding fibres in thermally non woven waves.
Generally, the two components must show good adhesion. however, side by side fibres can also be used for
producing the so called splitable fibres which split in a certain processing stage yielding fine filament of a sharp
edge cross section.

Figure 5. Schematic showing melt spinning of side by side bicomponent fibres


Multi layer fine or microfibres

After the commercialization of self-crimping bicomponent fibres in 1960s, attempts were made to multiply the
conjugating structure to produce much complicated bicomponent fibres, also sometimes referred to as multilayer
fibres. After development of multilayer fibres around 1965, the fibres were split (as shown in Figure 6) to
produce super fine fibres /microfibres

Figure 6. Evolution of Microfibres


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

Figure 7. Microfibre produced by separation/splitting


Segmented Pie

These are made from alternate wedges made from two different polymers. The number of wedges is around 16
to 32 and the spinning manifold is complicated. The fibre is drawn to high draw ratio and sometimes splitting
may occur while drawing.

The splitting is carried out by partial or complete dissolution of one component. Fibres obtained are of fine denier
and sharp cross section.

These are used for making non-woven web with ultra fine fibres. The resultant fabric is stronger and has higher
surface area.

Figure 8. Segmented pie bicomponent fibres

Figure 9. Schematic showing melt spinning of segmented pie structured fibres


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

Figure 11: Radial petal like conjugate fibres: a) without central hole and b) with central hole
Islands in the sea
These are also called as matrix-fibril fibres. In cross section there are areas of a polymer (island) in the matrix of
the other (sea).

Figure 12: Schematic showing melt spinning of islands in sea fibres


These are also used to produce finer fibres. Sheath is made up of a dissolvable material and core is made up of
desired material. Sheath is dissolved in proper solvent giving micro denier fibres.
Copyright IIT Delhi 2009-2011. All rights reserved.
MODULE 7. SMART/ FUNCTIONAL SPECIALTY FIBRES
7.4 Nanofibres by Electrospinning (2 Lectures)
Nanofibres and Electrospinning Process
What are Nanofibres?
Fibres finer than 500 nm are commonly referred to as nanofibres. When the diameter of polymeric fibres goes
down to sub-microns or nanometers, amazing characteristics such as very large surface area to volume ratio and
superior mechanical performance are observed.
As shown in Figure 1, the increase in surface area is as large as 103 times of that of a microfibre. This
increased surface area can result in a remarkable increase in capacity to attach or release functional groups,
absorbed molecules, catalytic moities, etc.

Figure 1.Dependence of surface area on fibre diameter


The strength increases because as the diameter reduces:
Defects go down
Orientation improves
Better formation of a fibrillar/compact structure
The flexibility also increasesas flexural rigidity is proportional to ( 1/ (diameter) 4)
In addition to above properties, the electrospun nanofibres form highly porous fibrous membrane with excellent
pore interconnectivity, controllability in fibre diameter morphology, ease of functionalization. Due to these unique
features, these fibres have potential for application in filter media, aerospace, capacitors, transistors,
biomaterials, barriers, wipes, personal care products, battery separators, energy storage, fuel cells, catalysts,
superabsorbent materials, composites, biosensor assembly and others. Some of the main applications of
nanofibres are discussed in later section.
Techniques of making nanofibres:

Nanofibres can be prepared by one of the following techniques

Drawing
Template synthesis
Self assembly
Phase separation
Electrospinning
Drawing is like usual dry spinning, can make long single nanofibres; with the limitation that, it is applicable
only for viscoelastic material that can undergo strong deformations while being cohesive enough to support the
pulling stress.
Template synthesis uses nano-porous membrane as template to make nanofibres. It cannot make single
continuous nanofibres.
Phase separation involves dissolution, gelation, extraction with solvent, freezing, drying; giving nanoporous
foam. It is relatively a longer time taking process.
Among all these, Electrospinning is recognized as the most efficient production technique. Mostly polymer
solution and sometimes polymer melts are used in this technique to produce nanofibres.
What is Electrospinning?
Electrospinning is a variation of electospraying process. This technique started gaining importance in 1994,
though the fundamental idea of electrospinning dates back to 1934.
Electrospinning is a fibre forming process which makes use of a high voltage electric field to produce an
electrically charged jet of polymer fluid, which on solidifying produces a nanofibre web typically with fibre
diameter from a few nanometres to few microns.
As shown in Figure 3, an electrospinning setup comprises of three main components:
A syringe pump for controlled delivery/flow of polymer fluid
A high voltage supply and
A grounded or oppositely charged collector
In electrospinning process, a high voltage electric field is applied to the end of the spinneret that contains the
polymer solution or a melt held by its surface tension. This creates a charge on the surface of the liquid. Mutual
charge repulsion and the contraction of the surface charges to the counter electrode cause a force directly
opposite to the surface tension as shown in Figure 2.

Figure 2. Forces acting on a droplet: Surface tension vs Electrostatic Charge


As the intensity of electric field is increased, the hemispherical liquid drop formed at tip of the capillary gets
distorted into conical shape called Taylor cone under simultaneous actions of repulsive force due to induced
surface charge and the attractive forces due to surface tension of the solution.
Figure 3. Schematic of Electrospinning set-up
Further increase in the potential beyond a critical voltage, a stable liquid jet ejects out and breaks up into
droplets due to surface tension for low viscosity liquids; hence the process is called as electrospraying.

Figure 4. Electrospraying mechanism


If the polymer used in the process is of higher molecular weight and its solution is made of considerable
viscosity, the jet from capillary tip travels to the grounded target without breaking up into drops; this process is
now known as electrospinning. The value of the critical voltage V depends on the properties of solution like
c

polymer molecular weight and solution viscosity. The charged polymer fluid jet undergoes an instability and
elongation process that allows the jet to become very long and thin. This stretching occurs due to the intensive
interaction of charged jet with the electric field. In this process, solvent evaporates and a charged nanofibres are
forms.

Figure 4. Fibre formation through electrospinning


Generally, the nanofibres formed by this process are obtained in the form of a random web and appear like a
very fine spray or a film as shown in Figure 5.
Figure 5. Nanofibre Web
If these are viewed in Scanning electron microscope, very fine random nanoweb is observed as shown in Figure
6.

Figure 6. SEM micrographs of electrospun web a) at lower magnification b) at higher magnification


( diameter~ 320 nm)
The versatility of electrospinning
The technique can be used to make nanofibres from a variety of polymeric materials such as high liquid
crystalline polymers, biopolymers or other composite materials. With advances in electrospinning process, core-
shell nanofibres can also be obtained. However, the electrospinning conditions are strongly influenced by the
characteristics of polymers. Most of these nanofibres were spun from solution, although spinning from the melt
in vacuum and air are also possible. Melt electrospinning requires special heating assembly to keep the polymer
in the molten form at the tip of the needle.
Table 1. Polymers spun by electrospinning
Polymer class Polymer Solvent
Polyimides Phenol
High performance
Polyamic acid m-cresol
polymers
Polyetherimide Methylene chloride
Polyaramid Sulphuric acid

Liquid crystalline Poly-gamma-benzyl


Dimethylformamide
polymers glutamate
Poly(-phenylene
Sulphuric acid
terephthalamide)
Nylon Formic acid

Textile fibre polymers Polyacrylonitrile Dimethylformamide


Trifluoroacetic acid and
Polyethylene terephthalate
dichloromethane
Electrical conducting
Polyaniline Sulphuric acid
polymer
Biopolymers DNA Water
Polyhydroxy butyrate-
Chloroform
valerate
Influence of electrospinning parameters:
The morphology of electrospun nanofibres is influenced by a number of parameters. The parameters can be
broadly classified into three categories:

The parameter related to solution properties are interdependent. For example any change in polymer
concentration,molecular weight and solvent composition affect the viscosity of a spinning dope.
In electrospinning for the fibre formation to occur, a minimum polymer concentration is required.Below this
critical value, application of voltage results in electrospraying and bead formation.

Figure 7. SEM Micrograph showing droplets and beads


As the polymer concentration is increased, a mixture of beads and fibres are formed. The spherical morphology
of beads gradually changes to spindle like and eventually uniform fibres are formed. The optimum
electrospinning concentration depends on the molecular weight and nature of polymer.This effect is observed
because of lower entanglement density. Entanglement density increases with increase in concentration,
molecular weight and nature of solvent (better solvent higher entanglement density).Too high entanglement
density results in thicker fibres.
Beads

Only Fibre
By varying the electrospinning parameters the morphology of the electrospun nanofibre web i.e. diameter,
deposition area and hence the porosity can be tuned. On twisting the bundle of nanofibres twisted nanofibre yarn
can be achieved.

Twisted nanofibre yarn


If cotton yarn is used as the collector, nanofibres can be deposited on the cotton yarn.By appropriate selection of
polymer solution and the substrates, different structures can be obtained.

Cotton yarn coated with nanofibres


Applications of Nanofibres:

As mentioned above, electrospun nanofibres have many unique characteristics, such as high surface-to-mass (or
volume) ratio, controllability in fibre diameter, surface morphology and fibrous structure, ability to form a highly
porous fibrous membrane with excellent pore interconnectivity, and are easy to functionalize. Because of these
unique features electrospun nanofibres can find applications in various fields. As shown in Figure 8, the
important applications of nanofibre are tissue engineering scaffolds,filtration, catalyst and enzyme carriers,
controlled release control, sensors, energy storage, membranes and recovery of metal ions.

Figure 8. Applications of electrospun nanofibres


In bioengineering area nanofibres can be used for tissue engineering, wound dressing, affinity membrane and
drug delivery. For tissue engineering and wound dressing, electrospun polymer nanofibres are treated as tissue
scaffolds which enhance cell growth and proliferation

Figure 9. SEM Micrograph showing cell growth on nanofibre made scaffold


The nanofibre scaffolds with seeded cells can be implanted to patient's body to repair the damaged tissues. For
drug delivery system, nanofibres are considered as a potential drug carrier.
The surface chemistry of nanofibres can be tailored to absorb toxic substances/molecules. Such structures can
be used for protective clothings
Biological Protective Clothing
Protective layer on fabric
With nanosized pores
Does not allow microbes, bacteria or viruses to pass
Protection against Chemical Warfare agents
Protection against toxic chemicals
Adsorption using activated surfaces of nanofibres
Nanofibres can be used in filters to remove very small particles and droplets. By incorporation of a thin layer of
nanowebs on conventional filters, the efficiency of filtration can be increased many folds for submicron particles
(MPPS: 0.1- 0.5 m). The comparison of structure of micron and nano filters, responsible for higher efficiency is
shown in Figure 10, less pressure drop and longer life.

Figure 10. Schematic showing micro and nano filters


Production of nanowebs
Despite enormous application potential, electrospun nanofibres have not been widely used in practice. The main
reason is that needle electrospinning has a very low nanofibre production rate, typically less than 0.3 g/hr. For
needle electrospinning, each needle nozzle normally generates one jet each time. As a result, the fibre
production rate is much lower than the requirement for commercial usage. Therefore the electrospinning setup
consisting of a single syringe can not be used for commercial production of nanofibres. For achieving higher
production rates, various approaches can be used.
A simplest solution is to increase the number of needles. Multiple syringe set-up for wide area deposition and
higher production rates can be used. However, intereferences due to electric field are required to be resolved.
Also, regular cleaning of each needle nozzle has to be carried out to prevent blockages.
Figure 11. Schematic showing multi-needle electrospinning
Several approaches have been used to increase the production rate of nanofibre formation:
Porous tubes: the pores were used to convey the polymer solution to tube surface,where the solution drops
were drawn under the action of high electric field.The process results in nonuniform nanofibres due to jet
intereferences.
Electrospinning from open liquid surface: In this technique, the free surface of liquid is used for generating
large number of spinning jets.Generally, rotating mettalic objects partially immersed in polymer solution are
used as spinnerets.A thin uniform layer of polymer solution is formed on the surface of spinneret due to its
rotation in the polymer solution. The spinnerets which are partially immersed in the spinning polymer solution
are connected to high voltage power supply.The rotation of the spinneret caused purturbations in the solution
layer resulting conical spikes on the surface of the solution.When the high voltage is applied, these spikes
concentrate the electric forces thus form taylor cones and jets are stretched from the taylor cones and result in
fibre formation.
The electrospinning process using this technique is difficult to control and it took nearly 45 years to patent a first
needleless electrospinning process. And it took another 25 years for this technique to mature and exhibit its
potential in mass production of nanofibres.
The geometry of spinneret is known to play a very crucial role on the quality of nanofibres formed. Various types
of spinneret geometries as shown below have been reportedly used for electrospinning.
Initially cylinder type spinnerets were commercialized. Several variations of cylinders have been reported in the
literature.

a) b)
Figure 12. Schematic showing cylinderical spinneret surface as spinneret for electrospinning a)
polymer solution distributed on cylinder and b) cylinder immersed and rotating in polymer solution
As electrospinning process involves use of high voltage for jetting of polymer solution, it was found that sharp
surfaces like disks when used as spinneret resulted in higher intensity electric field and showed better
performance in electrospinning.
Figure 13. Schematic showing disk surface as spinneret for electrospinning
Subsequent modification led to the use of spiral coil setup, which had higher production rate and better control
towards fibre morphology compared to disc and cylinder spinnerets.

Figure 14. Schematic showing spiral coil as spinneret for electrospinning


Very recently, a moving bead chain has been used as a spinneret. The mechanical vibration caused by moving
bead spinneret helps in initiating spinning jet.

Figure 15. Schematic showing moving beaded chain as spinneret for electrospinning
With the improved production rates, these fibres are being commercially exploited in many areas as discussed
above.
In addition to single component nanofibres, Core shell nanofibres and nanofibres reinforced with nanomaterials
are also being made for special end uses.

Copyright IIT Delhi 2009-2011. All rights reserved.