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The preparation, structure and properties of ultra-high modulus flexible polymers

  • I. M. Ward
Conference paper
Part of the Advances in Polymer Science book series (POLYMER, volume 70)

Abstract

In this review the preparation, structure and properties of ultra-high modulus polyolefins are discussed. First, detailed consideration is given to the preparation of ultra-high modulus polyethylene and polypropylene fibres by spinning from dilute solution and by gel-spinning and hot drawing. This is followed by an account of the tensile drawing procedures which have led to the production of high modulus fibres and films in polyethylene, polypropylene and polyoxymethylene. Finally, consideration is given in the production of high modulus solid section products (rod, sheet and tube) in all these polymers by ram extrusion, hydrostatic extrusion and die-drawing.

It is concluded that in these different processing routes the overriding consideration is to achieve very high extensional deformation at a molecular level. The structure of the initial isotropic polymer is therefore of key importance, the essential requirement being an adequate but not restrictive number of molecular entanglements, so that the molecular network can be stretched effectively to very high draw ratios and give very high molecular orientation. Molecular weight and morphology are therefore important, together with the drawing conditions which must permit sufficient mobility for the chains to move freely between network entanglements.

Following a review of present structural understanding of these highly oriented polymers, a detailed account is presented of mechanical behaviour, including dynamic mechanical relaxations, creep and strength. This is followed by discussion of thermal properties (melting behaviour, thermal conductivity, thermal expansion, shrinkage) and barrier properties (permeability to liquids and gases, solubility). It is of some practical importance that the improvements in stiffness and stength are accompanied by substantial improvements in thermal stability, in barrier properties and in chemical resistance.

Keywords

Draw Ratio Extrusion Ratio Deformation Ratio Tensile Drawing Hydrostatic Extrusion 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

List of symbols

B

Constant

c

Surface crack length

\(\mathop c\limits^*\)

Fitted constant

d

Fibre diameter

df

Die exit diameter

E

Young's modulus

Ec

Crystal modulus

Em

Modulus of Maxwell element

Ev

Modulus of Voigt element

Gc

Strain energy release rate

k

Boltzmann's constant

K

Thermal conductivity parallel to orientation direction

K

Thermal conductivity perpendicular to orientation direction

L

Long period

\(\bar L_{002}\)

Average crystal thickness

m

Constant

ms

Molecular weight of a statistical segment

Me

Molecular weight between entanglements

\(\bar M_n\)

Number average molecular weight

\(\bar M_w\)

Weight average molecular weight

Nc

Number of statistical chain segments between crosslinks

Ne

Number of statistical chain segments between entanglements

p

Probability of crystalline sequence linking two adjacent lamellae

P

Hydrostatic pressure

\(\mathop S\limits^*\)

Amorphous phase solubility

R

Deformation ratio at distance x from die cone apex

RA

Actual deformation ratio

RN

Nominal deformation ratio

t

Time

T

Absolute temperature

ΔU

Activation energy

v

Shear activation volume

vf

Die exit velocity

x

Distance from die cone apex

Y

Geometric factor

α

Die semi-angle

α0

Intrinsic thermal expansivity

α

Thermal expansivity parallel to orientation direction

ε

Strain

\(\dot \varepsilon\)

Strain rate

\(\dot \varepsilon _0\)

Pre-exponential factor

\(\dot \varepsilon _p\)

Plateau creep rate

\({\varepsilon \mathord{\left/{\vphantom {\varepsilon {\bar k}}} \right.\kern-\nulldelimiterspace} {\bar k}}\)

Lennard-Jones force constant

λ

Draw ratio

λmax

Maximum draw ratio

Φ

Polymer volume fraction

σ

Stress

σB

Breaking stress

σ0

Applied stress

σT

Tensile stress

τ

Retardation time of Voigt element

τf

Shear flow stress

Ω

Pressure activation volume

ηm

Viscosity of Maxwell element

ηv

Viscosity of Voigt element

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Copyright information

© Springer-Verlag 1985

Authors and Affiliations

  • I. M. Ward
    • 1
  1. 1.Department of PhysicsUniversity of LeedsLeedsUK

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