Dry-jet-wet spinning

Mukesh Kumar Singh

 Introduction
• Polymer is dissolved in an appropriate solvent to make the
fibre solution.
• This solution is then extruded under heat and pressure into
an air gap before it enters a coagulation bath.
• The produced fibre is then washed and dried before it is
heat treated and drawn.
• This is an alternative method to wet spinning and is
required as spinning directing into the bath
• For some fibres, creates microvoids that negatively affect
the fibre properties.
• this is due to the solvent being drawn out of the liquid too
quickly.
• An inert atmosphere may be required to prevent
oxidisation in some polymers, if so fibres are extruded into
a nitrogen atmosphere.
• This small difference in arrangement of spinneret (i.e.
placing it outside the coagulation bath) brings about
significant difference in spinning performance and ultimate
structure of the fibre.
• Dry-jet wet spinning imbibes the benefits of both dry
spinning and wet spinning.
• However unlike dry spinning, the air gap in dry-jet wet
spinning is too small to allow any appreciable removal of
solvent before the protofibres enter the coagulation bath.
• It is still sufficient to bring about changes on the surface of
the extruded filament.
• It is hypothesized that in PAN spinning, a kind of dense
cuticle (probably hydrophobic) is formed on the extruded
fibres as they pass through the air gap.
• This in turn changes the diffusion dynamics of the solvent
and nonsovent during the coagulation of the fibres
• This method is often required for high
performance fibres with a liquid crystal
structure.
• Due to their structural properties their melt
temperature is either the same as, or
dangerously close to their decomposition
temperature
• Therefore they must be dissolved in an
appropriate solvent and extruded in this
manner
 Benefits of dry-jet wet spinning
(a) High speed of spinning
(b) High concentration of dope
(c) High degrees of jet-stretch ratios
(d) Control of coagulation kinetics by monitoring
coagulation bath parameters.

Among these benefits, (a) to (c) are derived

because of the use of dry-jet and the air gap,
while (d) is derived from the use of wet coagulation.
 The diffusion coefficients of solvent and nonsolvent and their
relative values are extremely important in deciding the protofibre
structure.
The effect of various parameters on these diffusion coefficients in dry
jet wet spinning and immersion-jet wet spinning is explained below:

• Diffusion coefficients of solvent (DS) and nonsolvent (Dns) in both

cases are known to decrease with increasing dope concentration
and reducing coagulation bath temperature.
• However, diffusion coefficient of solvent is always larger than
diffusion coefficient of nonsolvent.
• This may be due to the higher affinity of the solvent to the
polymer matrix even though the size of the nonsolvent molecule
(such as water) is much smaller than that of solvent molecules
such as DMF, DMSO.
• Ratio of the two coefficients, DS/Dns increases with decreasing
temperature and with increasing concentration of the dope.
• This means that as the conditions for diffusion are made more
difficult, the differences between the solvent and non solvent
diffusion are markedly enhanced.
There are distinct differences between the
diffusion behaviour of solvent and nonsolvent in
dry-jet and immersion jet wet spinning.
• Diffusion coefficients for both solvent and non
solvent in dry-jet wet spinning are smaller than the
immersion-jet wet spinning.
• This is possibly because of the formation of more
dense structure of the entire protofibre or the
formation of cuticle on the surface of the protofibre
as it passes thorough the air gap in the dry-jet wet
spinning.
• However, the ratio of DS/Dns is always greater for
the dry-jet wet spinning than the immersion-jet.
Dry-jet-wet spinning of PAN fibre
Effect of jet-strech on diffusion coefficients of solvent (DS) and
non-solvent (D ns) for immersion-jet wet spun (IJWS) and dry jet
wet spun (DJWS) system
Mol orientation during dry-jet-wet spinning
Effect of jet stretch on diffusion coefficient ratio
for dry jet wet spun and wet spun system
• Jet-stretch ratio has a significant effect on diffusion
coefficients. The diffusion coefficient of solvent
increases and of water (non solvent) decreases with
increasing jet stretch ratio
• However, they both increase abruptly after a certain
critical jet stretch ratio in the immersion-jet wet
spinning possibly due to the formation of voids or
crevice openings on the fibre surface
• On the other hand, in dry jet wet spinning, the
diffusion coefficient of solvent keeps on increasing
and that of water keeps on decreasing with increasing
jet stretch ratio.
• This implies that on increasing jet-stretch ratio, the
ratio of DS/Dns increases rapidly in dry-jet wet
spinning resulting in a more compact and finer
filament structure without large voids.
• Therefore, dry-jet wet spinning is beneficial in making high
strength fibres, such as PAN precursors for carbon fibres,
where the formation of defect free structure of fine denier is
an essential requirement.
• A further advantage claimed for the dry-jet wet spinning
system is improved retention of cross-sectional shape so
that it is possible to spin filaments of controlled non-circular
cross-sections from orifices of appropriate shapes.
• The existence of even a small air gap has large influence on
the diffusion coefficients of solvent and nonsolvent,
however, the magnitude of the air gap has only a mild effect
on the diffusion coefficients in dry-jet wet spinning..
• Moderate increase in coagulation bath temperature
allows application of larger jet-stretch ratio.

• However, it leads to the formation of voids after a

certain critical jet-stretch ratio and the cross-section
of the fibre tends to become round.

• On the other hand, in dry-jet wet spinning, the

higher jet stretch ratio has no such detrimental
effect on protofibres rather it enhances the outward
movement of solvent compared to inward
movement of nonsolvent.
Effect of coagulation parameters