Mesophase pitch, processability

Fibers produced from pitch precursors can be manufactured by heat treating isotropic pitch at 400 to 450°C in an inert environment to transform it into a hquid crystalline state. The pitch is then spun into fibers and allowed to thermoset at 300°C for short periods of time. The fibers are subsequendy carbonized and graphitized at temperatures similar to those used in the manufacture of PAN-based fibers. The isotropic pitch precursor has not proved attractive to industry. However, a process based on anisotropic mesophase pitch (30), in which commercial pitch is spun and polymerized to form the mesophase, which is then melt spun, stabilized in air at about 300°C, carbonized at 1300°C, and graphitized at 3000°C, produces ultrahigh modulus (UHM) carbon fibers. In this process tension is not requited in the stabilization and graphitization stages. 

Because of their unique blend of properties, composites reinforced with high performance carbon fibers find use in many structural applications. However, it is possible to produce carbon fibers with very different properties, depending on the precursor used and processing conditions employed. Commercially, continuous high performance carbon fibers currently are formed from two precursor fibers, polyacrylonitrile (PAN) and mesophase pitch. The PAN-based carbon fiber dominates the ultra-high strength, high temperature fiber market (and represents about 90% of the total carbon fiber production), while the mesophase pitch fibers can achieve stiffnesses and thermal conductivities unsurpassed by any other continuous fiber. This chapter compares the processes, structures, and properties of these two classes of fibers. 

Fig. 7. Processing of carbon fibers from mesophase pitch.

The melt-spinning process used to convert mesophase pitch into fiber form is similar to that employed for many thermoplastic polymers. Normally, an extruder melts the pitch and pumps it into the spin pack. Typically, the molten pitch is filtered before being extruded through a multi-holed spinnerette. The pitch is subjected to high extensional and shear stresses as it approaches and flows through the spinnerette capillaries. The associated torques tend to orient the liquid crystalline pitch in a regular transverse pattern. Upon emerging from the... 

A very unusual characteristic of mesophase pitch is the extreme dependency of its viscosity on temperature [19,34,35]. This factor has a profound influence on the melt-spinning process (described above), as a mesophase pitch fiber will achieve its final diameter within several millimeters of the face of the spinnerette, in sharp contrast to most polymeric fibers. 

Liu, G. Z., McHugh, J. J., Edie, D. D. and Thies, M. C., Processing carbon fibers from three sources of mesophase pitch. In Carbon 92 Proceedings of International Carbon Conference, Essen, Germany, 1992, pp. 795 797. 

On the other hand, organic materials of relatively low molecular weight such as acetylene, benzene, ethylene and methane, can produce vapour-grown carbon materials by imperfect combustion or by exposing their vapour to a heated substrate in an electric furnace in the presence of a metal catalyst. The latter process generates VGCFs. Other precursors to VGCF include polyacrylonitrile (PAN), isotropic or mesophase pitch, rayon or nylon [8]. 

These methods, described above, are to produce material (still loosely called mesophase) which essentially is a feedstock for other process developments. This "mesophase" prepared at temperatures below normal carbonization temperatures can be called low temperature mesophase pitch (LTMP). The term mesophase pitch has crept into the vocabulary of this subject and is thought to refer mainly to mesophase as a feedstock. Its anisotropy can be detectable by polarized light optical microscopy. 

Based on the creation of naphthenic structures in the condensation reaction, the modification by aluminum chloride increased carbon yield and improved the potential for anisotropic development. Oxidative pretreatment usually impairs anisotropic development although it increases carbon yield. The oxidized pitch is also modified by aluminum chloride (34) this may be used to prepare additives (38) and mesophase pitches (39). It should be noted that these processes allow the catalyst to be readily separated (in contrast to catalytic carbonization) since the modified product is still either soluble in some solvents or fusible. 

As outlined earlier, the rheological properties of pitch and mesophase pitch are important in the processing of these materials to carbon products. The rheology of isotropic pitch will be considered briefly and then the effects of pyrolysis to mesophase will be described. 

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