Aramid Fibres

Mukesh Kumar Singh

High PERFORMANCE FIBRE
A fibre that is specially designed and
manufactured to give some specific
performance characteristics under some
specific ambient conditions
Example HM-HT Fibre
Kevlar, UHMWPE Fibre, PBO
Thermal resistant
Nomex, Kevlar, PBO, Carbon
History
Nomex -1960
Kevlar- 1971
Twaron (by Teijin ) 1980 by Ozawa &Matsuda
Last 20 years: structure and properties of
Aramid
Definition
United States Federal Trade Commission
1974
Aramid ia a manufactured fiber in which
the fiber 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.
p-phenylene terephthalarnide
(PTA), of which Kevlar fibres are made

Aramid manufacturing
By reaction between amine and carboxylic
acid halide group to synthesize AB
homopolymer

nNH
2
Ar COCl NH
2
Ar CO
n
nHCl
A
B
Similarly AABB homopolymer can also be
synthesized
Polymerization
Polycondensation
NH
2
NH
2
Poly-phenylene diamine (PPD)
ClCO ClCO
Terephthaloyl chloride (TCL)
Amide
solvent)
NH

NH

CO CO
2HCl
p-phenylene terephtalamides (PPTA)
Process
Dissolve PPD in a mixture of hexamythylphosphoramide (HMPA)
and N-methylpurrolidone (NMP)

Cooling in ice/ecetone to -15C in N
2
atmosphere

Add TCL with rapid stirring: paste like gel
Stand overnight with gradual warming to room temp

Resultant mixture is agitated with water to wash solvent and HCL
Polymer is collected by filteration
History of Aramid
Aromatic polyamides were first introduced
in 1960s, with a meta-aramid fiber
produced by DuPont under the tradename
Nomex.
Meta-aramid is also produced
Teijin: Conex
Kermel France: Kermel


Production
World capacity of para-aramid production
is estimated at about 41,000 tons/yr in
2002 and increases each year by 5-10%. In
2007 this means a total production
capacity of around 55,000 tons/yr.

Aramid Fibre Production
Polymer solvent for spinning PPTA is generally 100%
(water free) sulfuric acid (H
2
SO
4
).
The aromatic polyamide solution processing temperature is
of the order of 80C for the highly concentrated solution in
100% sulphuric acid.
At this temperature, the solution state corresponds to a
pneumatic crystalline phase. The degree of orientation of
these polymer chains depends on solution temperature and
polymer concentration. The radial crystalline orientation can
only be brought about using the dry-jet wet spinning process.
Kevlar fibres have a very high molecular orientation, which
has an almost directly proportional relationship to fibre
modulus and is highly dependent on drying conditions,
temperature and tension. By applying the above parameters
properly high tenacity Kevlar fibres can be obtained


Monomers are made up of fourteen
Carbon atoms, two Nitrogen atoms, two
Oxygen atoms and ten Hydrogen atoms.

A single Kevlar polymer chain could
possibly have anywhere from one to five
million monomers bonded together.


Kevlar
Kevlar is the trade name (registered by
DuPont Co.) of aramid (poly-para-phenylene
terephthalamide) fibers.
Kevlar fibers were originally developed as a
replacement of steel in automotive tires
Kevlar is high impact resistance and low
density fibre
Spinning
Solution is prepared by using H
2
SO
4
as
solvent (100% free from water)
Solution is heated to 80C
Solution solid content 10%

Liquid crystalline domains
S
p
i
n
n
e
r
e
t

Air gap
Elongational stretch
Coagulation bath
Gel spinning
Liquid crystalline solution

Semi-crystalline polymer
like nylon 6
Kevlar
Atomic configuration
a trans-amide
the peptide bond
carbonyl
carbon
amide
nitrogen
In the trans amide, the
Hydrocarbon group are on
opposite side of peptide bond
In the cis amide, the hydrocarbon
group are on the same side
of peptide bond
O
C
N
H
Properties of Kevlar Fibre
High tensile strength (five times stronger per weight
unite than steel)
High modulus of elasticity
Very low elongation up to breaking point
Low weight
High chemical inertness
Very low coefficient of thermal expansion
High Fracture Toughness (impact resistance)
High cut resistance
Textile processibility
Flame resistance (burning starts at 427C

0 5 10
15
20
1
2
3
4
Elongation (%)
S
p
e
c
i
f
i
c

s
t
r
e
s
s

(
N
/
t
e
x
)

Polyamide
Polyester
Steel
S-Glass
Aramid
Carbon-HS
HDPE
Moisture attraction by Kevlar
X-ray data have shown that the water
molecules from moisture uptake do not
enter the unit cell of the crystal lattice.
Hence, the amide-water molecular
interactions are likely to be confined to the
polymer chains on the surface.
Secondly, the presence of microvoids on
the surface
Limitations of Kevlar Fibre
Very low moisture regain
Very difficult to cut
Low compressive strength
Physical properties of materials
MATERIAL
Ultimate Strength
MPa
Density
g/cm
3

Spectra fiber (UHMWPE) 2300-3500 .97
Kevlar (ARAMID) 2757 1.44
Carbon Fibre 4137 1.75
Carbon laminate 1600 1.5
E Glass Fibre 3450 2.57
E Glass laminate 1500 1.97
Polypropylene 19.7-80 .91
S Glass Fibre 4710 2.47
Spider Silk 1000 1.3
Steel alloy ASTM A36 400 7.8
Epoxy 12-30 1.23
Nylon 75 1.15
Modulus of materials
Material
Young's Modulus
GPa
PTFE (Teflon) 0.5
Rubber (small strain) 0.010.1
PTFE (Teflon) 0.5
Low density polyethylene 0.2
UHMWPE (such as Dyneena or Spectra) .7
Polypropylene 1.5-2
Nylon 24
Pine wood (along grain) 8.963
Glass-reinforced plastic (70/30 by weight
fibre/matrix, unidirectional, along grain)
4045
Carbon fiber (depends on direction and type) 300-400
Carbon fiber reinforced plastic (70/30
fibre/matrix, unidirectional, along grain)
181
Steel 200
Single-walled carbon nanotube 1,000+
Molecular requirement of Aramids
Improvement Polymeric composition
Thermal resistance Wholly aromatic polyamide, absence of
unstable linkage (urethane, urea, alkylene etc.)
Solubility Copolymer with dissymmetrical units inclusion
of O-, -CO-, -SO
2
- etc., amides rather than
esters
Drawing potential High molecular weight
Enhanced chain flexibility by incorporating -O-,
-CO-, -SO
2
-, etc
Dimensional
stability
Rigid molecular chain, crystallinity
Chemical properties of Kevlar
Aramid Fibers are Chemically quite
Resistant
Aramids are not sensitive to organic solvents or oil.
Kevlar, Twaron and other Aramids are sensitive to strong acids, bases, and
certain oxidizers, like chlorine bleach* (sodium hypochlorite).
Exposure to these cause degradation of the fiber.
Regular chlorine bleach (e.g. Clorox) cannot be used with Kevlar, oxygen
bleaches such as sodium perborate (e.g. OxiClean) can be used without
damaging the Aramid fiber.
Hydrogen Peroxide cannot be used to whiten Aramid though.
This is important for anyone cleaning boat ropes or sails containing Kevlar.
Polyester (Dacron) is not particularly sensitive to bleach but Kevlar's
strength will be destroyed! Nylon is also attacked by bleach
Most organic solvents (oil) have little effect on the material, and most salt
solutions (sodium chloride) have no effect on Kevlar fiber. However, strong
acids and bases (hydrochloric acid and sodium hydroxide) at high
concentrations or elevated temperatures are able to attack Kevlar fiber.

Types of Kevlar fibre
Kevlar 29 high strength (3600 MPa), low density
(1.44 g/cc
3
), used for bullet-proof vests, composite
armor reinforcement, helmets, ropes, cables,
asbestos replacing parts

Kevlar 49 high modulus (131 GPa), high strength
(3800 MPa), low density (1.440 g/cm) used in
aerospace, automotive and marine applications

Kevlar 149 ultra high modulus (186 GPa), high
strength (3400 MPa), low density (1.470 g/cm)
highly crystalline, used as reinforcing dispersed
phase for composite aircraft components.

a trans-amide a cis-amide
O
C N
H
O
C N
H
In Nomex the aromatic group are linked into the
Molecular chain through 1 and 3 positions
(i.e meta-linkage)
O
C N
H
O
C N
H
In Kevlar the aromatic group are linked into the
Molecular chain through 1 and 4 positions
(i.e para-linkage)
n
C
N
O
H
C
N
O
H
C
N
O
H
C
N
O
H
C
O
All trans polyamide stretches fully to
form a wonderful Aramid fibre, Kevlar
Fibre axis
Applications of Kevlar
Kevlar may protect carbon fibers and improve their
properties: hybrid fabric (Kevlar + Carbon fibers)
combines very high tensile strength with high
impact and abrasion resistance

The most popular matrix materials for
manufacturing Kevlar (aramid) Fiber Reinforced
Polymers are Thermosets such as Epoxies (EP),
Vinylester and Phenolics (PF)

Kevlar Fiber Reinforced Polymers are manufactured
by open mold processes, closed mold processes and
Pultrusion method
Aramid Brands
Nomex
Aramid fibre reinforced for sealing friction
Conveyor belts
Technora Sulfron
Aramid fibre: Kevlar
Aramid Brands
Aramid /PVC: Clad for optical fibre
Aramid fibre honeycomb
Aramid fibre braided sleeve Sharx
Ultra-High-Molecular-Weight-Polyethylene
(UHMWPE) fibers

C C
H
H
H
H
n
N=40,000
Solvent for UHMWPE: Decaline
Thanks