4.3 Wet Spinning

Fibers produced by wet spinning include rayon and Kevlar. Rayon was originally developed as a synthetic substitute for silk and Kevlar was produced as a high-strength fiber for use in various aerospace and specialty-use applications. Furthermore, many comercial acrylic fibers are also produced by wet spinning.



As with dry spinning, the polymer is dissolved or suspended in a solvent, to form a viscous "spin dope" and filaments are formed by extrusion through tiny holes in a spinneret plate. Kevlar, for example, will degrade thermally if attempts are made to melt it, and thus a solvent must be used. The term wet spinning more accurately depicts the process than does dry spinning, because the solvent is extracted or, perhaps more appropriately, leached, from the filaments by another liquid. In most cases, the second liquid is aqueous.

A major difference between wet spinning and either melt or dry spinning is that one is spinning into a fluid (liquid) with a much higher viscosity. Because this higher viscosity can translate into high shearing stresses on the surfaces of the filaments, the tension in the filaments can become quite high. For example, towing a buoy by a long line behind a boat can produce very high tensions in the line when compared with towing the same buoy by a short line. For long baths, the tension can become sufficiently high that the filaments might break, as their tensile strength is exceeded. To avoid this danger, much lower spinning speeds must be used. Whereas melt spinning may utilize spinning speeds of 2,000 yards per minute (80 mph), spinning speeds in wet spinning are usually less than 300 ypm.

Another difference with dry spinning is the capability of using many more spinneret holes in the case of wet spinning. The total number can approach 60,000 in a single spinneret plate, if the spinning is done directly into a coagulating or extracting liquid. Because the liquid is present, the filament forms a type of skin almost immediately and the potential for the filaments to touch and fuse is practically eliminated, compared with dry or melt spinning.

In the case of Kevlar the spin dope is relatively warm, about 100°C, and forms a viscous, liquid crystal. The solvent is sulfuric acid, at a concentration of about 80 wt% (20 wt% polymer). These liquid crystals are easily oriented by a stretching motion, but they can lose their orientation, presumably by Brownian motion, once the stretching is stopped. Therefore, during the spinning process, the filaments are first extruded through an air gap, where the filaments undergo strains of 2 to 3x, which produces a high degree of molecular orientation in the filaments, and then they are suddenly "quenched." This air gap is of the order of one inch. It also allows the spinneret plate to be warm (100°C) while the extraction bath can be cool (ca 15°C). The hot filaments then strike the cooling bath where the filaments are quenched and much of the orientation is locked in by the rapid cooling action. Subsequent to the quench step, the solvent is extracted, which requires a relatively long bath contact time. But the initial quenching step is crucial, since it allows for the oriented molecules to be "frozen" into position. This orientation is particularly important to the high-strength properties of Kevlar-the filaments, on a weight basis, are significantly stronger that steel. If one attempts to use the same process to produce Kevlar filaments of large diameter, the core of the filaments can lose its orientation, because the quench time to reach the core will increase with the square of the filament radius. The filament skin, or the outer part of the filaments, however, will have the orientation locked in and a high degree of orientation will exist there. This produces a so-called "skin-core" effect, in which the average properties of the filaments, expressed as tensile strength per unit cross-sectional area, will decline on account of a decreased average orientation.

Kevlar, with its focus on strength development via "air-gap" wet spinning, is somewhat unique within the process of wet spinning. As with melt- and dry- spinning, the controlling part of the process is associated with development of the filament structure, either by cooling of the filament or by removal of the solvent. The equations for diffusion in wet spinning are identical to those for dry spinning, with the exception that the fluid passing outside the filaments is a liquid and not a gas. Also, the flow may not be across the filaments, but even, partially, along the filaments. Therefore, the correlations and nature of the flow surrounding the filaments will result in different values for the surface mass transfer coefficient. Whether this will change the relative resistance dramatically will depend on the particular fiber to be produced and its dimensions and properties. Note that the same graphical solutions described earlier can be used.

To design a wet-spinning process, it may be necessary to predict the transport of momentum, heat, and mass in the region adjacent to the filament just downstream of the spinneret. One can use a so-called "boundary-layer" analysis to do this. Treatment of such an analysis is beyond the scope of the present discussion of fiber spinning, but a brief description of the analysis is appropriate. One form of boundary-layer analysis involves von Karman integral boundary-layer techniques. The boundary layer starts at zero thickness at the first point where the fiber contacts the extracting liquid, and grows gradually radially outwards from each filament as one proceeds downstream. The velocity profile inside the boundary layer is assumed and all of the velocity change between the filament and the surrounding fluid is contained within this "momentum" boundary layer. Similarly, thermal and diffusional boundary layers contain all the changes in temperature and concentration, respectively. Based upon approximations of these velocity profiles, frequently assumed to be turbulent, the variation in filament drag with position can be predicted, along with local heat and mass transfer coefficients. The student is referred to the text Transport Phenomena, by Bird, Stewart, and Lightfoot, Wiley, New York (1960) for additional details of such integral boundary-layer techniques.

Key elements of the wet spinning process include:

Similarity of governing equations to melt and dry spinning,

Lower spinning speeds in wet spinning,

Structure development in air-gap spinning of Kevlar and skin-core effects,

Qualitative introduction to boundary-layer concepts.