Aramid

Fibers

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Outline
Introduction
Types of Aramid fibers
Preparation of fibers
✔ Polymerization
✔ Extrusion into filaments
✔ Orientation of fibers
Fiber heat treatment
Structure of aramid fibers
Properties of aramid fibers
✔ Chemical Properties
✔ Thermal properties
✔ Mechanical properties

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 Introduction
The term “aramid” is short for “aromatic polyamide”.
- 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”.
- These fibers have much superior mechanical properties than steel and glass
fibers on an equal weight basis, and maintain these properties at high
temperatures.
- They are good replacement for metal wires and inorganic fibers in some high
performance applications by definition.
- The aramid family will cover kevlar, nomex, technora, teijinconex,
twaron fibers.
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 Types of Aramid fibers

Poly (p benzamide) Poly (m-phenylene isophthalamide)

(Twaron) MPDI (Nomex)

Poly(p-phenylene terephthalamide) Copolymer (Technora)

PPTA or PPDT
(Kevlar) 4
Structural difference between Polyamide and Aramid

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 Preparation of fibers
Polymerization
Extrusion into filaments
Preparation of staple fibers
Polymerization
- These are generally prepared by low temperature solution polycondensation of
various aromatic amines and diacids or diacid chlorides.
- The usual melt polycondensation methods for the preparation of aliphatic
polyamides are not suitable
- The preferred solvents are dimethyl acetamide (DMAc), N-methyl-2-
pyrrolidone
(NMP), hexamethyl phosphoric triamide (HMPA), tetramethyl urea (TMU).

Terephthaloyl chloride (TCl) p-phenylene diamine (PPD) 6

Polymerization

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 Extrusion into filaments
Dope Structure
- The linear aramid molecular structures, such as PBA and PPD-T are Nematic liquid
crystals
- The liquid crystal state is a distinct phase between the crystalline (solid) and
isotropic (liquid) states
- Molecular bundles (mesogens) point along a common axis, called the director

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 Extrusion into filaments
The aramids decompose before they melt, therefore, they are
produced by dry jet wet spinning methods and wet spinning

Wet spinning
- The spinneret is immersed in coagulation bath
- The extruded fibers coagulate immediately without alignement of
domains
- The mechanical properties are not that good

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 Extrusion into filaments
Dry jet-wet spinning
- Improved properties are achieved using dry-jet-wet spinning technique

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 Extrusion into filaments
The polymer dope (in concentrated sulphuric acid) is extruded through spinnerets at
about 90 °C through about 1 cm air gap into coagulation bath.
- The fiber precipitates in the air gap and the acid is removed in the coagulation bath
- The spinneret capillary and air gap cause rotation and alignment of domains
resulting in highly crystalline and oriented as-spun fibers

- When the polymer solutions passes through the

capillary hole, the capillary shear causes some of
the liquid crystal domains to orient along the
direction of shear
- The fiber is highly oriented and does not require a
subsequent drawing process, as is required for
conventional fibers.
- The attenuated filament, after washing, neutralization
and drying results in highly crystalline, high strength,
high modulus fiber
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 Orientation of fibers

Schematic of Crystalline Orientation of para-aramid fiber:

(a) random; (b) radial; (c) tangential.
- Using dry-jet wet spinning radial crystalline orientation is obtained.

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 Fiber heat treatment
The physical and tensile properties of spun aramid fibers can be further improved
by heat treatment under tension.

- In wet spun yarns, both tenacity and modulus

increase exponentially with increasing
temperature (and draw ratio).
- 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 but the tenacity remains constant.
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 Structure of aramid fibers
Aramids particularly Kevlar can acquire a high degree of alignment of long straight
polymer chains parallel to fiber axis due to the liquid crystalline domains orientation and
alignment in flow direction

Kevlar fiber contains several levels of superimposed microscopic and macroscopic

structures including the crystal lattice, pleated structure, fibrillar structure and skin-core
structure.

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 Structure of aramid fibers

The sheets are held together in Kevlar fibers by the 'random' but 'continuous'
intermolecular forces between adjacent layers of molecules.
- The molecules form a planar array with inter-chain hydrogen bonding.

- The stacking sheets form a crystalline array, but between the sheets the bonding is
weak

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 Properties of aramid fibers

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 fiber
axis direction lead to a great mechanical property anisotropy.

The functional properties of aramid fibers, particularly tensile properties are

related to the fiber structure at molecular level.

The polymer chain rigidity, crystalline orientation and crystallinity are the
key properties governing the final fiber properties.

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Properties of aramid fibers

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 Properties of aramid fibers
Aramid fibers are characterized by medium-to-ultrahigh strength, medium-to- low
elongation and moderately high-to-ultra high modulus with the densities for crystalline
fibers ranging from 1.35 to 1.45 g/cm3.

Fibers of low orientation MPD-I (e.g. Nomex) have a density of 1.35 g/cm3 fibers from
PPD-T (e.g. Kevlar) have a density of ~ 1.45 g/cm3

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

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 Chemical properties of aramid fibers
Moisture absorption
- The hydrophilicity of amide linkage leads to moisture absorption by all aramids.
- In addition to chemical composition, fiber structure also plays a critical role in
determining the moisture absorption.

Chemical resistance
- Very good chemical resistance to the attack of organic solvents and aqueous salt
solutions.
- Strong acids and bases do attack the fiber at elevated temperatures, causing hydrolysis
of
amide linkage and loss of strength.
- These fibers are more resistant to acids than nylon 6,6 fibers, but not as resistant as
polyester fibers.
Dye-ability
- Aramid fibers are exceedingly difficult to dye by conventional methods due to their
very
high Tg.

UV stability
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- The aromatic nature of p-aramid is responsible for a substantial absorption of UV light,
 Thermal properties of aramid fibers

Aramid fibers do not melt in the conventional sense because decomposition

occurs simultaneously.
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.
Excellent thermo-stability 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 conjugation between the amide groups and the aromatic ring in p-aramids
is responsible for the yellow color and increased chain rigidity which help
into excellent retention of physical properties at elevated temperature.

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 Mechanical properties of aramid fibers

Typical stress-strain curve of Kevlar aramid yarn as compared to other

industrial filament yarns.

The outstanding high strength of Kevlar can be

attributed to:

- Its aromatic nature and amide group.

- High crystallinity and orientation.

- Individual polymer strands of Kevlar are held

together by H-bonds that form between the polar
amide groups on adjacent chain.

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 Mechanical properties of aramid fibers

Bending strength

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 Mechanical properties of aramid fibers

Comparison of Aramid with other

fibers

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 Mechanical properties of aramid fibers
Compressive strength
- When subjected to axial compression, the fiber 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)

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 Mechanical properties of aramid fibers
Compressive strength
- The compressive buckling of the aramid molecules is by molecular rotation
of
the amide C-N bond

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 Mechanical properties of aramid fibers

Fatigue
- Aramid like Kevlar have excellent Fatigue behavior.
- With tension fatigue no failure is observed even at loads as high as 60% of
breaking strength and 107 cycles.

Creep
- These fibre exhibit very low creep even at elevated temperature.
- At a load of 0.5 of breaking load after 105 sec, creep strain for Kevlar is only
0.3%.

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Application of aramid fibers

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Application of aramid fibers

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