Phenolics Fiber reinforcement

Bisphenol A. One mole of acetone condenses with two moles of phenol to form bisphenol A [80-05-07] which is used mainly in the production of polycarbonate and epoxy resins. Polycarbonates (qv) are high strength plastics used widely in automotive appHcations and appHances, multilayer containers, and housing appHcations. Epoxy resins (qv) are used in fiber-reinforced larninates, for encapsulating electronic components, and in advanced composites for aircraft—aerospace and automotive appHcations. Bisphenol A is also used for the production of corrosion- and chemical-resistant polyester resins, polysulfone resins, polyetherimide resins, and polyarylate resins. 

Most processors of fiber-reinforced composites choose a phenol formaldehyde (phenoHc) resin because these resins are inherently fire retardant, are highly heat resistant, and are very low in cost. When exposed to flames they give off very Htde smoke and that smoke is of low immediate toxicity. PhenoHc resins (qv) are often not chosen, however, because the resole types have limited shelf stabiHty, both resole and novolac types release volatiles during their condensation cure, formaldehyde [50-00-0] emissions are possible during both handling and cure, and the polymers formed are brittle compared with other thermosetting resins. 

In addition to electrical uses, epoxy casting resins are utilized in the manufacture of tools, ie, contact and match molds, stretch blocks, vacuum-forrning tools, and foundry patterns, as weU as bench tops and kitchen sinks. Systems consist of a gel-coat formulation designed to form a thin coating over the pattern which provides a perfect reproduction of the pattern detail. This is backed by a heavily filled epoxy system which also incorporates fiber reinforcements to give the tool its strength. For moderate temperature service, a Hquid bisphenol A epoxy resin with an aHphatic amine is used. For higher temperature service, a modified system based on an epoxy phenol novolak and an aromatic diamine hardener may be used. 

One of the interesting properties of PBPCP [187] was its fast heat dissipation characteristics and so it was tested by the well-known oxy-acetylene panel test (ASTM 285-70) for ablative materials. Figure 13 shows the survival of a flower for 100 s. kept on the 6.35-mm asbestos fiber-reinforced hexamine-cured panel. The ablation rate value of this material was 3.2 x 10 in/s in comparison with 3.6 x 10 in/s for asbestos-phenolic. As the char content of PBPCP was only 27% compared with 60% for conventional phenolics, mechanisms involving transpiration processes rather than heat blocking by char formation might be playing a greater role in this case [188]. 

Fig. 2-59 Surface heat balance of an ablating glass fiber reinforced phenolic plastic.

One typical example of carbon/carbon composite plates is that made by Oak Ridge National Laboratory (ORNL) in the United States [12]. The composite preform was fabricafed by a slurry-molding process from fhe mixed slurry befween short carbon fibers (graphite fibers were also added in some sample plates) and fhe phenolic resin. The mass rafio between fiber reinforcement and phenolic matrix is 4 3. The phenolic matrix improves the mechanical properties and dimensional stability of the plate. A subsequent vacuum molding process was utilized to fabricate composite plates and fluid fields with relatively high resolution (Figure 5.3, [11]). 

Carbon Composites. Cermet friction materials tend to be heavy, thus making the brake system less energy-efficient. Compared with cermets, carbon (or graphite) is a thermally stable material of low density and reasonably high specific heat. A combination of these properties makes carbon attractive as a brake material and several companies are manufacturing carbon fiber—reinforced carbon-matrix composites, which are used primarily for aircraft brakes and race cars (16). Carbon composites usually consist of three types of carbon carbon in the fibrous form (see Carbon FIBERS), carbon resulting from the controlled pyrolysis of the resin (usually phenolic-based), and carbon from chemical vapor deposition (CVD) filling the pores (16). 

Some of the common types of plastics that are used are thermoplastics, such as poly(phenylene sulfide) (PPS) (see POLYMERS CONTAINING SULFUR), nylons, liquid crystal polymer (LCP), the polyesters (qv) such as polyesters that are 30% glass-fiber reinforced, and poly(ethylene terephthalate) (PET), and polyetherimide (PEI) and thermosets such as diallyl phthalate and phenolic resins (qv). Because of the wide variety of manufacturing processes and usage requirements, these materials are available in several variations which have a range of physical properties. 

The matrix can be either a thermoset or thermoplastic. The oldest and still widest used material for compression molded products is phenolic. The thermoset materials used to manufacture fiber reinforced compression molded articles is unsaturated polyester sheet or bulk, reinforced with glass fibers, known as sheet molding compound (SMC) or bulk molding compound (BMC). In SMC, the 25 mm long reinforcing fibers are randomly oriented in the plane of the sheet and make up for 20-30% of the molding compound s volume fraction. 

Fiber reinforced plastics (FRP) are widely utilized now for a number of cryogenic applications. The matrices used are generally thermosetting resins such as epoxies, polyesters and phenolics, since they are easy to apply in impregnating processes. 

Since 1958, an extensive experimental literature has developed, primarily on epoxies, and, to a lesser extent, on polyesters, polyimides, phenolics, and other resins. Work in this area has been greatly stimulated by the increasing importance of thermosets as matrix resins in fiber reinforced composites, and by significant improvements in instrumentation and measurement methods. 

High density charring ablators such as carbon-phenolic contain high density reinforcements to improve shear resistance. In contrast, lower density charring ablators as a rule are used for low shear environments. Hie Apollo mission reentry conditions are typical of a relatively low shear environment, so low density ablators consisting of epoxy—novolac resin containing phenolic microballoons and silica fiber reinforcement have been used. In order to improve the shear resistance and safety factor of the material for this mission, the ablator was injected into the cavities of a fiberglass -reinforced phenolic honeycomb that was bonded to the substructure of the craft (48). 

Carbon fiber reinforced ceramic composites also find some important applications. Carbon is an excellent high temperature material when used in an inert or nonoxidizing atmosphere. In carbon fiber reinforced ceramics, the matrix may be carbon or some other glass or ceramic. Unlike other nonoxide ceramics, carbon powder is nonsinterable. Thus, the carbon matrix is generally obtained from pitch or phenolic resins. Heat treatment decomposes the pitch or phenolic to carbon. Many pores are formed during this conversion from a hydrocarbon to carbon. Thus, a dense and strong pore-free carbon/carbon composite is not easy to fabricate. 

Substrates used included fiber-reinforced epoxy base polymer [FRP], nylon 66, polytetrafluoroethylene [Teflon], poly(ethylene terephthalate) [PET], phenolic resin, and thermoplastic polyimide [ULTEM, GE]. FRPs were the primary substrates used. Initially, they were cleaned with detergent in an ultrasonic bath followed by rinsing with deionized water and alcohol. For further cleaning, they were treated with oxygen plasma (1.33 seem, 60 W, 5 min) followed by a hydrogen plasma treatment (3 seem, 60 W, 5 min). 

S. J. Park and Y. S. Jang, Interfocial characteristics and fiacture toughness of electrolytically Ni-plated carbon fiber-reinforced phenolic resin Matrix composites, J. Colloid Interface Sci. 237 (2001) pp. 91-97. 

Bradford, I. Synthesis and Characterization of a Novel Brominated Phenolic Resin for Glass Fiber-Reinforced Composites. M.S. Thesis, Tuskegee University, Aug 2002. 

This chapter will deal with the chemistry and applications of epoxies, phenolics, urethanes, and a variety of current vogue high-temperature polymers. Applications in fiber-reinforced plastics will be discussed in the individual sections on resin chemistry where appropriate. Separate sections will deal with adhesives and sealants. Adhesives are most important because, as early history demonstrates, they led the way to the application of resins in aerospace. A section is also included on silicone and polysulfide sealants. Although these materials are elastomers rather than resins, no discussion of aerospace polymers would be complete without some mention. Some major thermosetting polymers have been omitted from this review. Among these are the unsaturated polyesters, melamines, ureas, and the vinyl esters. Although these products do find their way into aerospace applications, the uses are so small that a detailed discussion is not warranted. 

Chen, F. and Jones, F. R., Injection moulding of glass fibre reinforced phenolic composites 1. Study of the critical fibre length and the interfacial shear strengtli, Plast., Rubber Composites Proc. Appl, 23, 241 (1995). Termonia, Y., Structure-property relationships in short-fiber-reinforced composites, J. Polym. Set, Polym. Phys. Ed., 32, 969 (1994). 

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