Gel-Spun

High Performance

Polyethylene

Fiber

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Outline
Introduction
Molecular Character
Gel Spinning
Gel Spinning Process
Gelation and Crystallization
Drawing
Fiber Characteristics
Fiber Form
Structure and Morphology
Fiber Properties
Physical Properties
Tensile Properties
Mechanical Properties in the transverse direction
Applications
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 Introduction

 Gel-spun polyethylene fibres are ultra-strong, high-modulus fibres that are based on the
simple and flexible polyethylene molecule.

- High-performance polyethylene (HPPE) fibres

- High-modulus polyethylene (HMPE) fibres,
- Extended chain polyethylene (ECPE) fibres

- Owing to low density and good mechanical properties, the

performance on a weight basis is extremely high.

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 Introduction

With the increase in molecular weight, the

mechanical properties of polymers also
increase.

The processing of higher molecular

weight polymers is difficult by
conventional methods.

The mechanical properties of fibers of

polyethylene obtained by conventional
methods are lower than the estimated
extended chain structure based on the
bond strength.

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 Introduction
 For producing the high performance polyethylene (HPPE) an ultra-high
molecular weight (UHMW-PE) is used as the starting material.
- The ultra high molecular weight PE is a
preferred starting material from point of
defect reduction.

- In aramids and comparable fibers, the

molecules tend to form rod-like structures and
these need only be oriented in one direction to
form a strong fiber.

- Polyethylene has much longer and flexible

molecules and only by physical treatments can
the molecules be forced to assume the straight
(extended) conformation and orientation in the
direction of the fiber.
- Drawing is necessary for straightening and orientation
of chains. 5
 Introduction

 The melt spinning of such a high molecular material is not possible due to the
extremely high melting point and viscosities.

 The drawing of the melt processed UHMWPE is only possible to a limited

extent due to presence of very high degree of chain entanglements

 The molecular chains are unable to move freely with respect to each other, and
therefore, cannot be unfolded.

 But for proper orientation, a sufficient amount of entanglement is also

necessary

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 Molecular Character

 Gel-spun high-performance polyethylene fibres are produced from polyethylene with

a very high molecular weight (UHMW-PE).

 This material is chemically identical to normal high-density polyethylene (HDPE),

but the molecular weight is higher than the commonly used PE grades.

 It is in the range that is used in abrasion-resistant engineering plastics.

 All the physical and chemical properties of polyethylene remain in the fibres.

 The differences result from the high chain extension (stretching), the high

orientation and the high crystallinity.

 The gel-spun fibres have properties that are superior to those made by

solid-state processes.
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 Gel Spinning
 If the entanglement of chains is very low, they will be difficult to be drawn.
 If polymer chains are very long and flexible, the entanglement will also be very high
due to which it will be difficult to process by conventional method.

 For making high performance fibers from flexible polymers, the spinning process
should be modified in such a manner that it allows formation of fully extended and
oriented polymer chains.
 In gel spinning process, the polymer solution is prepared at temperature and
conditions where it is flow-able and is extruded to conditions where it forms a gel
structure.

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 Gel Spinning Process

 The main steps of the gel spinning process are:

- Polymer dissolution to prepare a homogeneous dope (Extrusion)

- Spinning of a solution of ultra high-molecular weight polyethylene (UHMW-
PE)
- Gelation and crystallization of the UHMW-PE
- Done either by cooling and extraction or by evaporation of the solvent.
- Super drawing and removal of the remaining solvent

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 Gel Spinning Process
 Various solvents, such as tetralin, decalin, naphthalene, mineral oil, paraffin
oil and paraffin wax, have been reported for gel spinning of UHMWPE.

- 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.

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Gel Spinning Process

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 Gel Spinning Process

 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. This phenomenon is known as 'pull-out.

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 Gel formation or Crystallization
 After the removal of solvent, the fibers 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
fiber.

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 Drawing
 The final properties of the fiber in the gel-spinning process are achieved in the
super drawing stage

- The strength and modulus are directly related to the draw ratio.

- The maximum attainable draw ratio appears to be related to the molecular

weight and the concentration.

- Drawing up to a very high draw ratio (50–100 times).

- Melt processed UHMW-PE can be drawn up to five times only.

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 Fiber Characteristics

 Fiber form

 Gel spun High performance polyethylene is available under the trade

names Dyneema and Spectra and is produced as a multifilament
yarn.
 The titre of the monofilaments varies from about 0.3 denier per
filament (dpf) (0.44 dtex) to almost 10 dpf (11 dtex).
 Tenacity of one filament may well be over 5 N/tex, and the modulus can
be over 120 N/tex.

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 Fiber Characteristics

 Structure and morphology

 The fiber is highly crystalline; the crystallinity is typically >80%.

 The crystal domains are highly extended in the fiber direction.
 The crystal domains are organized in nano- or micro-fibrils, which in turn
form macro-fibrils.

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Fiber Physical Properties

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 Fiber Tensile Properties

 The primary properties of the Dyneema and Spectra fibres are high strength

and high modulus in combination with the low density.

 HPPE fibers have a density slightly less than one, so the fiber floats on water.

 The tenacity is 10 to 15 times that of good quality steel and the modulus

is second only to that of special carbon fiber grades.

 Elongation at break is relatively low, as for other high-performance fibers,

but owing to the high tenacity, the energy to break is high.

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 Fiber Tensile Properties
 Textile units (N/tex) relate the strength to the weight of the fiber whilst
engineering units (GPa) refer to the cross-section and the volume of a fiber.
 It is clear from this diagram that the combination of low density and high
strength makes Dyneema and Spectra unique products.
 HPPE fibres are not only first choice in weight saving, but that their use can also
give volume saving.

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Fiber Tensile Properties

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 Fiber Tensile Properties
 The areas below the curves are the energy-absorbing capacities of the fibers.

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 Fiber Tensile Properties
Dyneema and Spectra would in theory reach to a satellite’s orbit

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 Mechanical properties in the transverse direction

 As all the chains in the fiber are aligned in the fiber direction, the

mechanical properties are highly anisotropic.

 In the transverse direction the modulus and strength are much

lower than that in the fiber direction.

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 Viscoelasticity

 Polyethylene is a viscoelastic material, that is, the properties depend

significantly on such variables as temperature and loading history.
 The mechanical properties of HPPE fibers such as tensile strength (or
tenacity), tensile modulus and elongation at break depend on the
temperature and the strain rate
 The Creep increases with loading time, resulting both in a lower modulus and
a higher strain at rupture.
 Creep values are not the same in all HPPE fibers but depend on choices
made in the production process.
 Energy Absorption

 Dyneema and Spectra fibres can absorb extremely high amounts of energy.
 This property is utilized in products for ballistic protection.
 The fiber is equally suited for products such as cut-resistant gloves and
motor helmets.
 Fatigue
 HPPE fibers are the first high-performance fibers that not only have a
high tenacity but that also have tension and bending fatigue properties
comparable with the commonly used polyamide and polyester grades in
ropes.
 The high strength polyethylene fiber is quite resistant to repeated axial
loading.
 The relatively low melting temperature makes the fiber sensitive to
warming- up
 High-speed loading and relaxation may lead to high temperatures, but a
thick rope immersed in water may stand the test without any difficulty.
Fatigue
 Chemical Properties

 Abrasion Resistance
 The HPPE fibers also have good abrasion resistance
 It determines wear and tear and so the service life.
 Due to very high abrasion resistance, it is used for gloves.

 Effects of water
 Polyethylene is not hygroscopic and does not absorb water.
 The fibers have a very low porosity, therefore water absorption in the fiber
is negligible.
 The multifilament yarns used as strands in a rope or in a fabric, typically
have 40% void.
 Therefore, water can be absorbed between the fibers.
 If that is not acceptable, water repellent additives should be used.
 Polyethylene fibers do not swell, hydrolyze or otherwise degrade in
water, seawater or moisture.
 Chemical Properties
 Chemical resistance
- HPPE fibers are produced from polyethylene and do not contain any aromatic
rings or any amide, hydroxylic or other chemical groups that are susceptible to
attack by aggressive agents.
- The result is that polyethylene and especially highly crystalline, high molecular
weight polyethylene is very resistant against chemicals.
- Dyneema and Spectra fibers, being of a polyolefinic nature, are sensitive to oxidizing
media.
- In strongly oxidizing media, fibers will lose strength very fast.
 Chemical Properties

 Resistance to Light and other Radiation

 Electrical properties
 Polyethylene is an insulator and has no groups with dipole character.
 As-spun yarns contain a small fraction of spin oil of a hydrophilic nature.
 So, for applications where the electrical properties are important, the spin
finish should be removed.
 Acoustic properties
 As with all mechanical properties, the acoustic properties are strongly
anisotropic.
 In the fiber direction, the sound speed is much higher 6 times faster than
transverse direction.

 Biological resistance
 The biological resistance of the fiber is that of high-density polyethylene.
 The fiber is not sensitive to attack by micro-organisms.

 Toxicity
 Polyethylene is regarded as biologically inert.
 Thermal Properties

 Thermal resistance
 Dyneema has a melting point between 144 and 155°C, depending on the
conditions.
 The tenacity and modulus decrease at higher temperatures but increase at
sub-ambient temperatures.
 The mechanical properties are influenced by the temperature and the main
reason is thought to be chain slippage, that is polyethylene chains that move
relative to each other in the direction of the fiber.
 Thermal Properties

 Fire properties
 Dyneema and Spectra fibers have a LOI index lower than 20, which simply means that

they can burn in atmospheric conditions.

 HPPE fibers are polyethylene, a thermoplastic material that melts at about 150°C and

decomposes over 300°C.

 The toxicity of the gases in a fire depends on:

 The composition of the substrate; if the material contains nitrogen, sulphur or

chlorine (or any other halogen), such as polyamides and aramids, the gases are
always toxic.
 Given the composition, the conditions in the fire are by far the main
parameters for the development of toxic gases. The local
temperature and oxygen concentration determine which gases are produced.
 Shrinkage

 Due to high extension, the molecular chains contract in order to return to

the thermodynamically preferred coiled conformation.

 Shrinkage is negligible below 100°C, and will occur mainly between 120 °C

and 140°C.
 Applications

 Ballistic Protection

 Cut and Puncture Resistance

 Low Speed Impact

 Twines and Nets

 Ropes