Kinetics of solution spinning

In wet spinning, the rheology and mechanics dictate mostly the stability and to a lesser
extent the orientation of the system, whereas kinetics of coagulation are important in
controlling the morphological structure of the spun fibre and its ultimate physical
properties.

In coagulation during wet spinning, solvent from the fibre diffuses out of the extruded
filament and the nonsolvent from the coagulation bath diffuses into the fibre. As the
nonsolvent interacts with the polymer solution, the homogeneous polymer solution
undergoes phase separation into polymer rich and polymer lean regions (i.e. liquid-
liquid demixing). With time, as more and more coagulant enters the filament, polymer
comes out of the solution. The rates at which the solvent moves out and the non solvent
moves in decide the rate of coagulation or kinetics of coagulation. The individual rates
of diffusion of solvent and nonsolvent and their ratio (relative diffusion expressed in
terms of ratio of diffusion coefficients) decide the thermodynamics of the process, and
hence, the internal structure of the forming fibre (Figure 1).

The final morphology (i.e. the state) of the phase separated protofibre is decided solely
by the thermodynamics of the process. However, kinetics decides the rate at which the
morphology is allowed to change. Therefore, the faster is the diffusion of solvent-
nonsolvent, the higher is the likelihood of having defects in the coagulated fibre. At high
temperature, the fluxes of solvent and nonsolvent are nearly equal and protofibre
maintains a round shape with large voids . However, with decrease in temperature, the
ratio of diffusion coefficients of solvent (D S) and nonsolvent (DNS) increases and the
cross sectional shape of the protofibres turns more towards bean shape.
 Figure 1: The effect of coagulation kinetics on morphology of the protofibres.

If the concentration of the coagulation bath (i.e. conc. of solvent in the bath) is lowered,
the concentration gradient of the solvent between the fibre and the bath increases, and
the diffusion flux becomes higher, pushing the coagulation to a higher rate. Therefore, in
order to keep the coagulation rate at a lower level, the temperature and concentration of
the bath are maintained towards lower and higher values, respectively.

In dry spinning, nonsolvent is not involved. The solvent diffuses out of the protofibre into
the heated gas atmosphere. The fibre does not enter the phase separation region, and
therefore, there are no voids in the spun fibre and the structure is compact. Kinetics of
solvent removal do not have much bearing on the properties of dry spun fibres,
however, it influences its cross-sectional shape in a big way. If the rate of diffusion of
solvent from core to surface of the fibre is higher than or equivalent to rate of mass
transfer from surface to the surrounding hot gas, then the fibre shrinks slowly and
uniformly forming a round cross section. However, when the rate of mass transfer from
surface to surroundings is faster than the diffusion of solvent from core to the surface,
then dog-bone shaped cross-section is obtained. This happens because faster removal
of solvent from the surface results in the formation of crust that fixes the circumference
of the fibre in the initial stages of the spinning. The subsequent removal of solvent from
inside of the fibre collapses the fibre with fixed circumference in a symmetrical fashion
to give dog-bone shape.

Electrospinning

Electrospinning is a fiber production method which uses electric force to draw charged
threads of polymer solutions or polymer melts up to fiber diameters in the order of some
hundred nanometers. Electrospinning shares characteristics of both electrospraying and
conventional solution dry spinning of fibers. The process does not require the use of
coagulation chemistry or high temperatures to produce solid threads from solution. This
makes the process particularly suited to the production of fibers using large and
complex molecules.

The most basic set up for this technique involves a solution contained in a reservoir
(typically a syringe) and tipped with a blunt needle (for needle-based electrospraying), a
pump, a high voltage power source and a collector. The spinning process starts when
the solution is pumped at a constant flow rate and a specific voltage is applied to create
an electric field between the needle tip and the collector. A charge accumulates at the
liquid surface. When the electrostatic repulsion is higher than the surface tension the
liquid meniscus is deformed into a conically shaped structure known as the Taylor cone.

When a sufficiently high voltage is applied to a liquid droplet, the body of the liquid
becomes charged, and electrostatic repulsion counteracts the surface tension and
the droplet is stretched; at a critical point a stream of liquid erupts from the surface. This
point of eruption is known as the Taylor cone.
Figure 2 : Electro spinning process
 Post Spinning Operation

Introduction to drawing

As spun fibres have poor elasticity (inability to recover) and they undergo plastic
deformation on application of low levels of stress. This makes them unsuitable for any
application including that of apparel. The polymer chains in the as-spun fibres are in
partially folded conformation and can extend easily on application of stress. Figure 3
shows a stress-strain plot of an as-spun fibre. The elastic region is small and is bound
by the yield point that occurs at a low stress and extension level. Following the yield
point, the fibre shows deformation without much resistance till all the chains are
unfolded and a new improved (more elastic) network of polymer is formed. In this
region, the polymer chains assume new extended conformation and do not recover
back to their original state when stresses are released. This is known as the region of
‘natural draw’ and the extensibility is called “Natural draw ratio (NDR)” of the fibres. This
region of easy extensibility must be removed to make the fibres stable and show the
behaviour of increasing resistance with increasing extension.

Figure 3: Stress-strain curves for (A) as-spun and (B) spun-drawn fibre.
Drawing is necessary to remove the region of natural draw of the fibres. When the fibre
is drawn beyond the NDR, polymer chains form an elastic network with extended
conformation in the direction of draw (i.e. along the fibre axis). This gives fibres higher
yield point, strength, initial modulus, and recovery compared to its as-spun form. Figure
1 also shows a typical stress-strain plot of a drawn fibre in comparison to that of an as-
spun fibre. Maximum draw ratio (MDR), in contrast, is the maximum extensibility a fibre
may be subjected to, before it breaks.

Drawing Machines

Drawing is carried out by simply stretching the filament yarn between two sets of rollers.
A typical drawing machine is shown in Figure 4. The drawing occurs between feed
rollers and take-up rollers (Draw rollers) at room temperature or at an elevated
temperature by providing a heater plate. The drawn material is given a small twist and is
wound on a bobbin as shown in Figure. The path of the yarn undergoing drawing is
regulated by proving guide pins or alternately placing the feed and take-up (drawing)
rollers perpendicular to each other. An idler roller at an angle is provided with each roller
set (i.e. feed or draw) to allow the yarn to be wound in multiple loops separately on each
on these rollers. This gives a better grip to the yarn and the yarn does not slip easily
under drawing tension.

The ratio of the surface speed of the draw (V2) and feed roller (V1) is called the
'machine draw ratio'. The fibre after drawing may relax and recover some part of the
machine draw ratio applied to it. Eventually, the fibre may attain a draw ratio called
'actual draw ratio', given by final length to the initial length, which is equal to or less than
the machine draw ratio depending upon the amount of relaxation the fibre undergoes.
The speed at which the fibre travels between the two rollers determines the rate of
drawing. An estimate of this draw rate can be worked out as follows:

The average speed between the rollers is (V1 + V2)/2; if the distance between the draw
rollers is L, then the time spent by the fibre during drawing is t= L / (V1+V2)/2.
Figure 4: Schematic diagram of a typical drawing frame.