Precursor fibers

Process. Any standard precursor material can be used, but the preferred material is wet spun Courtaulds special acrylic fiber (SAF), oxidized by RK Carbon Fibers Co. to form 6K Panox B oxidized polyacrylonitrile (PAN) fiber (OPF). This OPF is treated ia a nitrogen atmosphere at 450—750°C, preferably 525—595°C, to give fibers having between 69—70% C, 19% N density less than 2.5 g/mL and a specific resistivity under 10 ° ohm-cm. If crimp is desired, the fibers are first knit iato a sock before heat treating and then de-knit. Controlled carbonization of precursor filaments results ia a linear Dow fiber (LDF), whereas controlled carbonization of knit precursor fibers results ia a curly carbonaceous fiber (EDF). At higher carbonizing temperatures of 1000—1400°C the fibers become electrically conductive (22). 

The precursor fiber is subsequently washed and stretched to the low tex (denier) required for carbon fiber processing. Stretching also imparts considerable orientation to the polymer molecules and provides the basis for the highly oriented carbon stmcture that forms after carbonization. Special care is taken to avoid contamination or impurities that may form strength reducing flaws in the carbon fiber. 

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. 

The cyclotrisilazane (R = Me) produced in reaction (14) is recycled at 650°C [by reaction with MeNHo) the reverse of reaction (14)] to increase the yield of processible polymer. Physicochemical characterization of this material shows it to have a softening point at 190°C and a C Si ratio of 1 1.18. Filaments 5-18 pm in diameter can be spun at 315°C. The precursor fiber is then rendered infusible by exposure to air and transformed into a ceramic fiber by heating to 1200°C under N2- The ceramic yield is on the order of 54% although, the composition of the resulting amorphous product is not reported. The approach used by Verbeek is quite similar to that employed by Yajima et al. (13) in the pyrolytic preparation of polycarbosilane and its transformation into SiC fibers. 

Figure 1. Melt spun BN precursor fibers, magnification 500x.

Carbon/graphite fibers are prepared from either a polyacrylonitrile or rayon precursor fiber or from a pitch precursor 22,23). In either case, the fibers are treated at high... 

Not only must precursor fibers be self-supporting as extruded, they must also remain intact (e.g. not melt or creep) during pyrolytic transformation to ceramic fibers. Thus, precursor fibers (especially melt spun fibers) must retain some chemical reactivity so that the fibers can be rendered infusible before or during pyrolysis. Infusibility is commonly obtained through reactions that provide extensive crosslinking. These include free radical, condensation, oxidatively or thermally induced molecular rearrangements. 

As we shall see in the chapters to follow, melt or solution spinning is perhaps the most common method of giving a fibrous form to a material. Even in the case of ceramic fibers that are produced from polymeric precursor fibers, high speed... 

A boron nitride fiber can be very competitive commercially with carbon fiber. It has about the same density (2.2 g/cm ) as the carbon fiber, but has greater oxidation resistance and excellent dielectric properties. A method of converting boric oxide precursor fibers into boron nitride fibers has been developed (Economy and Anderson, 1967). Melt spun boric oxide precursor fiber is nitrided with ammonia according to the following reaction ... 

Polyacrylonitrile (PAN) precursor fibers are more expensive than rayon. Nevertheless, PAN is more commonly used because the carbon fiber yield is about double that from rayon. Pitch-based carbon fibers are also important, because, potentially pitch is perhaps the cheapest raw material. Table 8.2 shows that carbon yield is highest from the mesophase pitch. The reader is cautioned that this is true only if we exclude the losses during the mesophase conversion step. If, however, one compares the overall carbon fiber yield from raw pitch to that from PAN, then the yield from PAN is higher. In any event, the carbon fiber yield or precursor weight loss is a very important factor in the economics of processing. 

Excluding the losses in the initial mesophase conversion step before precursor fiber preparation. 

Polyacrylonitrile (PAN) is the most common precursor used to make carbon fibers. A flow diagram showing the steps involved in making PAN-based carbon fiber is shown in Fig. 8.3. The PAN precursor has a flexible polymer chain structure like any other polymer, but it has an all carbon backbone chain that contains polar nitrile groups, as shown in Fig. 8.4. During the stabilization treatment, the PAN precursor fiber is heated to 200-220 C, under tension. When this is done oxygen is absorbed, and it serves to cross-link the chains the fibers turn black, and a stable ladder structure is formed. A ladder polymer is a rigid... 

Amoco has developed a family of ultra high modulus continuous graphite fibers and preforms with axial thermal conductivity to llOOW/mK. The extremely high thermal conductivity is a direct result of an extremely high degree of crystallinity during carbonization of the mesophase pitch precursor fiber. Table... 

FIGURE 56 SEM micrographs for PVP-precursor fibers (A) and La2Zr207 fibers calcined at 1000 °C (B). Reprinted with permission from Li et al. (2006b). Copyright 2006 Elsevier. 

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