High Strength High Modulus Fibers

Introduction
 The fundamental science of structure-property relationship developed
in aramids has been further extended to form other aromatic and
heterocyclic rigid rod polymers.
 These polymers include:
 Melt-spun wholly aromatic polyester
 PBO and related polymers
 PIPD or ‘M5’ rigid-rod polymer
 Russian aromatic fibers
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
 Thermotropic liquid crystal polymer
 ‘Liquid crystal’ is a term given to an organic polymer that exhibits
order similar to an ordinary solid crystal
 When viewed in the molten state on a hot stage microscope
through polarising lenses, this polymer is called a ‘thermotropic
liquid crystal polymer’
 These polymers consist of very rigid, chain-like molecules that
position themselves into randomly oriented domains.
 When these domains are extruded through very small holes, the
flow and accompanying shear aligns the domains parallel to each
other in the direction of flow
 When cooled down, the extruded fiber has a highly oriented
structure with high tensile strength and modulus.
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
 Thermotropic liquid crystal polymer
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
 Vectran
 Vectran, is produced from Vectra LCP polymer.
 It is obatined from polymerisation of p-hydroxybenzoic acid and 6-hydroxy-
2-naphthoic

 Vectran is the only commercially available melt spun LCP fiber in the world.
 Research and development for the polymers and fibres were focused on tyre
cord, to compete with para-aramids.
 When a cost advantage with these TLCP polymers could not be realised in

tyre cord, emphasis shifted towards resin development for electronics parts
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
 Vectran
 Vectran is known for its exceptional properties like;
 High strength and modulus
 Excellent creep resistance
 High abrasion resistance
 Excellent flex/fold characteristics
 Minimal moisture absorption
 Excellent chemical resistance
 Low coefficient of thermal expansion (CTE)
 High dielectric strength
 Outstanding cut resistance
 Excellent property retention at high/low temperatures
 Outstanding vibration damping characteristics
 High impact resistance
High Strength High Modulus Fibers
Vectran
 Measurement System For Vibration Damping
High Strength High Modulus Fibers
Vectran

Vectran• Aramld

8 c
i... 0 ·-
0

..a .t.a! 0
s
0.0 Times 250.0 ms 0.0 Times 250.0 ms
Carbon Fibers Glass Fibers
c c
0 0
:;:; i O
..s
. fa O
>·- s
0.0 Times 250.0ms 0.0 Times 250.0 ms
Periodic Damping of Single Fibers Reinforced Composite
(Matrix Resin: Epoxy)
CKRC)
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
 Vectran (Fiber production)
 With conventional polyesters, the molecular chains are random and
flexible.
 Fibers spun from such materials must be further oriented, generally through

a combination of extrusion speed and post-spin drawing, to obtain higher
tensile properties
 Vectran is highly oriented structure is locked in directly during the melt

spinning process, thanks to the molecular structure and liquid crystalline
nature of the starting polymer.
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
 Vectran (Fiber production)
 TLCP fiber is melt spun using conventional polyester extrusion practices
 Attention to uniform polymer flow is essential.
 Wind-up speed is much lower, as is draw down, compared with PET
processes.
 Typical physical properties for the spun product are 10 g/denier tenacity
(0.9 N/tex), 2% elongation, and 425 g/denier initial modulus (40 N/tex)
 High strength, 23–28 g/denier tenacity (2–2.5 N/tex), is achieved in TLCP
fibers by heat treating in an inert atmosphere
 The fiber is produced as a continuous filament.
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
Vectran (Fiber properties)
 Tensile Properties
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
Vectran (Fiber properties)
 Thermal Properties
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
Vectran (Fiber properties)
 Thermal Properties

Strength At High Temperatures: Strength After Thermal Exposure

Simultaneous Mechanical and Thermal Loading 24 Hour Exposure To Temperature, Followed by
Testing at Ambient Temperature
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
Vectran (Fiber properties)
 Chemical Resistance
 Vectran fiber has good strength retention in chemical exposures covering a

wide range of aggressive chemicals, concentrations, exposure times, and
temperatures
 The fiber is resistant to organic solvents, some acids of >90%
concentration, and bases of <30% concentration.
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
Vectran (Fiber properties)
 Creep

Creep Behavior At Ambient Temperature (30% of Break Load)

High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
Vectran (Fiber properties)
 Stress Relaxation
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
Vectran (Fiber properties)
 UV Resistance
High Strength High Modulus Fibers
Melt-spun wholly aromatic polyester
Vectran (Fiber properties)
 Abrasion Resistance
High Strength High Modulus Fibers
Fibers based on Aromatic Heterocyclic Polymers
 Heterocyclic rigid-rod polymers can be classified into three categories
 Polybenzazole
 Polybenzimidazole

 Polybenzazole
 Polybenzazole polymers abbreviated as (PBX) include polybenzothiazoles (PBT) and
polybenzoxazoles (PBO)

The key structural feature of these two polymers

is the formation of the benzothiazole and
benzoxazole ring structures.

Polybenzimidazole
High Strength High Modulus Fibers
Fibers based on Aromatic Heterocyclic Polymers
 Synthesis 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.

Trans-PBT is based on 2,5-diamino-1,4-

benzene-dithioldihydrochloride (DABDT) and
TA

The polymerization is carried out in poly

(phosphoric) acid (PPA) solvent

Molecular weights of about 50000-100000

g/mol corresponding to about 200-400
repeat units per chain are obtained.
High Strength High Modulus Fibers
Fibers based on Aromatic Heterocyclic Polymers
 Polybenzazoles fiber production
Rigid rod polymers decompose at high temperatures without melting and can be
dissolved in very few solvent systems owing to their aromatic structure and to their
rigid molecular backbone
Conventional melt-spinning and solution-spinning technologies cannot therefore be
used

These fibers can be spun from solutions in PPA via the dry-jet wet-spinning technique
High Strength High Modulus Fibers
Fibers based on Aromatic Heterocyclic Polymers
 Structure of Polybenzazoles fibers

The crystallites are well aligned parallel to the fibre axis

The fiber contains hierarchical structures which comprise macrofibrils, fibrils, and
microfibrils, with typical diameters of 5, 0.5 and 0.05mm, respectively.

The microfibrils consist of crystallites in combination with amorphous or disordered

regions
High Strength High Modulus Fibers
Fibers based on Aromatic Heterocyclic Polymers
 Properties of Polybenzazoles fibers
 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
High Strength High Modulus Fibers
Fibers based on Aromatic Heterocyclic Polymers
 Properties of Polybenzazoles fibers
High Strength High Modulus Fibers
Fibers based on Aromatic Heterocyclic Polymers
 Properties of Polybenzazoles fibers
 Effect of post treatment on Modulus of PBO fibers

As = As spun fibers

HM= Heat treated

fibers

HM+ = Non aqueous

coagulation bath
High Strength High Modulus Fibers
PIPD or ‘M5’ rigid-rod polymer
 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

Poly(2,6- pyridinylene-1,4 (2,5-dihydroxy)

phenylene) (PIPD) or M5
High Strength High Modulus Fibers
PIPD or ‘M5’ rigid-rod polymer
 The structure of PIPD or M5 is similar to PBO and PBT except for the
following differences
 The central aromatic ring in M5 is pyridinyl rather than benzyl
 Presence of hydroxyl groups at 2-and 5-positions of diacid and
 The X group in benzazole ring structure is NH.
High Strength High Modulus Fibers
PIPD or ‘M5’ rigid-rod polymer

Structure of Kevlar Structure of M5

High Strength High Modulus Fibers
PIPD or ‘M5’ rigid-rod polymer
 Properties
High Strength High Modulus Fibers
Russian aromatic fibers
 The main reactants that were investigated by Russians for the
development of high performance fibers are following
High Strength High Modulus Fibers
Assignment