0 Bewertungen0% fanden dieses Dokument nützlich (0 Abstimmungen)
25 Ansichten6 Seiten
Carbon fibers are on the brink of broad commercialization. Their use is growing rapidly, fueled by price reductions and increasing availability. Carbon fiber composites are now being adopted in fields such as automotive, civil infrastructure.
Carbon fibers are on the brink of broad commercialization. Their use is growing rapidly, fueled by price reductions and increasing availability. Carbon fiber composites are now being adopted in fields such as automotive, civil infrastructure.
Carbon fibers are on the brink of broad commercialization. Their use is growing rapidly, fueled by price reductions and increasing availability. Carbon fiber composites are now being adopted in fields such as automotive, civil infrastructure.
CARBON FIBERS, after a 40 year period of development and use in specialized applications, are now on the brink of broad commercializa- tion. Their use is growing rapidly, fueled by sig- nicant price reductions during the 1990s and increasing availability. Changes in the perfor- mance/price ratio have resulted in the increased penetration of composites into applications for- merly held by metals and has enabled their use in other applications previously not possible with existing materials. Additionally, market conditions increasingly favor designs for com- mercial products that are lighter, stronger, faster, and more fuel efcientdesigns that are possi- ble with carbon bers. No longer relegated to aerospace, carbon ber composites are now be- ing adopted in elds such as automotive, civil infrastructure, offshore oil, and paper produc- tion. History The earliest commercial use of carbon bers is often attributed to Thomas Edisons carboni- zation of cotton and bamboo bers for incandes- cent lamp laments (Ref 1). However, practical commercial use of carbon bers for reinforce- ment applications began in the late 1950s with the pursuit of improved ablative materials for rockets (Ref 2). Union Carbide marketed a car- bonized rayon based fabric in the early 1960s (Ref 3). DuPonts work with black Orlon in the late 1950s showed that acrylics could be ther- mally stabilized, while Shindo in Japan and Watt et al. in the United Kingdom demonstrated that, by using tension through the carbonization pro- cess, high mechanical properties could be real- ized (Ref 4). Activity increased rapidly during the 1960s and 1970s to improve the performance/price ra- tio of carbon bers. Much of this effort focused on evaluation of various precursors, since carbon ber can be made from almost anything that yields a quality char upon pyrolysis. Donnet and Bansal (Ref 5) present a good overview of vari- ous researchers efforts to evaluate different pre- cursors, including PAN (polyacrylonitrile), pitch, rayon, phenol, lignin, imides, amides, vi- nyl polymers, and various naturally occurring cellulosic materials. Overall carbon ber demand grew to approx- imately 1000 metric tons by 1980, fueled pri- marily by the aerospace industry, with the sport- ing goods industry taking some excess capacity and off-specication ber. Polyacrylonitrile- based carbon ber usage had exceeded all other precursors at that time. This was a surprise to some, since the anticipation in the late 1970s had been that the signicantly lower raw material price and higher char yield of pitch would result in the winning combination. However, higher processing costs are required to make a spinna- ble pitch, so better overall properties for PAN bers resulted in their dominance. Rayon was relegated to third place, despite having a lower rawmaterial cost, because inferior properties and a low char yield (20 to 25%) after carbonization made for a higher overall cost. Properties can be improved by stress graphitization at high tem- peratures, but this increases cost further, making the ber even less desirable. Rayon is still used today for insulating and ablative applications but not for structural applications. By the mid-1990s, a new cost-effective, PAN- based carbon ber made from a modied textile precursor was being aggressively promoted by companies like Zoltek and Fortal for commer- cial applications. In 1995, one manufacturer an- nounced the goal of reaching a price level of $5/ lb ($11/kg) by the year 2000, which brought alot of attention to and greatly accelerated applica- tion development (Ref 6). An overall trend of improved performance/price ratio for both pitch and PAN ber manufacturers has sustained this growth. Carbon ber demand has grown to an esti- mated 16 10 6 kg (35 10 6 lb) per year (Ref 7). Usage in 1997 was estimated at 30% aero- space, 30% sporting goods, and 30% commer- cial/industrial applications, with the industrial applications poised for the greatest growth (Ref 8). Manufacture of Carbon Fibers Precursor sources used, in order of volume, are PAN, pitch, and rayon. Although the specic processing details for each precursor is different, all follow a basic sequence involving spinning, stabilization, carbonization, and application of a nish or sizing to facilitate handling, as shown in Fig. 1. Discontinuous carbon ber whiskers are also now produced in a batch process from Fig. 1 The processing sequence for polyacrylonitrile (PAN) and mesophase-pitch-based precursor bers shows the similarities for the two processes. Highly oriented polymer chains are obtained in PAN by hot stretching, while high orientation in pitch is a natural consequence of the mesophase (liquid crystalline) order. This article is from ASM Handbook, Volume 21, Composites
Copyright ASM International, 2001
It is reproduced by permission of ASM International,
www.asminternational.org. All rights reserved. Additional information about ASM Handbook, Volume 21 is available at www.asminternational.org 36 / Constituent Materials hydrocarbon gases using a vapor-liquid-solid growth mechanism. PAN-based Carbon Fibers. The majority of all carbon bers used today are made from PAN precursor, which is a form of acrylic ber. Pre- cursor manufacture is accomplished by spinning the PAN polymer into laments using variants of standard textile ber manufacturing pro- cesses. The PAN bers are white in color, with a density of approximately 1.17 g/cm 3 (0.042 lb/ in 3 ) and a molecular structure comprised of ori- ented, long chain molecules. Stabilization in- volves stretching and heating the PAN bers to approximately 200 to 300 C (390 to 570 F) in an oxygen-containing atmosphere to further ori- ent and then crosslink the molecules, such that they can survive higher-temperature pyrolysis without decomposing. Stretching after spinning and during stabilization helps develop the highly oriented molecular structure that allows devel- opment of a high tensile modulus and improved tensile strength upon subsequent heat treat- ment. Carbonization of standard and intermediate modulus ber typically involves pyrolyzing the bers to temperatures ranging from1000 to 1500 C (1800 to 2700 F) in an inert atmosphere, typ- ically to a 95% carbon content. An additional high heat treatment step is included just after car- bonization for some very high-modulus bers. During carbonization, the bers shrink in diam- eter and lose approximately 50% in weight. Re- straint on longitudinal shrinkage helps develop additional molecular orientation, further increas- ing mechanical properties. After carbonization, the bers may be run through a surface treatment step designed to clean and attach functional groups to the ber surface, which increases bond strength with ma- trix resins. Most manufacturers use an electro- lytic oxidation process that creates carboxyl, car- bonyl, and hydroxyl groups on the surface for enhanced bonding. A sizing or nish is then ap- plied to minimize handling damage during spooling and enhance bonding with matrix res- ins. The ber is then spooled. Today, there is differentiation among manu- facturers between those who use a modied tex- tile-type PAN precursor and those who use an aerospace-type precursor. The textile-type pre- cursor is made on a very large scale in modied- acrylic textile ber plants in tows or rovings con- sisting of 200,000 laments. The tows are then split down into smaller bundles (approximately 48,000 laments) after carbonization for spool- ing. Aerospace precursor is made in smaller spe- cialty plants and processed in 3000 (3K) to 12K lament tows that can be assembled into 24K or larger tows after carbonization. Manufacturing cost is lower for the textile-type precursor, due to higher line throughputs, larger economies-of- scale, and less handling of smaller tow bundles. This type ber is more targeted for industrial ap- plications. The aerospace-type precursor, be- cause it is processed in smaller tow sizes, is less fuzzy and available in the small tow sizes fa- vored by the aerospace industry, for whom it was originally developed. Physical properties can be similar for both types. Pitch-Based Fibers. Pitch is a complex mix- ture of aromatic hydrocarbons and can be made from petroleum, coal tar, asphalt, or PVC (Ref 9). Starting raw material selection is important to the nal ber properties. Pitches must be pro- cessed through a pre-treatment step to obtain the desired viscosity and molecular weight in prep- aration for making high-performance carbon - bers. The pre-processed pitch contains meso- phase, a term for a disk-like liquid crystal phase (Ref 10) that develops regions of long-term or- dered molecules favorable to manufacture of high-performance bers. Without this step, the result is an isotropic carbon ber with low strength and low modulus of less than 50 GPa (7 10 6 psi) (Ref 11). Process details of the nal composition and method of spinning me- sophase pitch are generally held secret by the manufacturers. Once spun, the stabilization, carbonization, surface treatment, application of sizing, and spooling of pitch-based bers follows a se- quence similar to the manufacture of PAN-based bers, as shown in Fig. 1. Actual process param- eters, such as temperatures, ramp rates, and time at temperature for stretch and stabilization, are different for pitch than for PAN. Gas species evolved during pyrolysis and their onset of evo- lution are very different for PAN and pitch. The response to heat treatment is also greater for me- sophase-pitch-based bers at higher tempera- tures, a consequence of their more ordered start- ing molecular structure. For example, a mesophase-pitch-derived ber processed to the same temperature as a PAN ber will exhibit higher density and thermal and electrical con- ductivity, all else being equal. Other Precursors. Rayon is processed in similar fashion to PAN, as shown in Fig. 1; the difference is the actual process parameters used. Carbon ber whiskers can be formed from gas-phase pyrolysis via catalyzed cracking of hy- drocarbon gases like methane. One process in- volves growth of a thin carbon tube of 10 to 50 nm from a submicron iron particle in a hydro- carbon-rich atmosphere, followed by a second- ary process of thickening the tube by chemical vapor deposition of carbon on the surface (Ref 12). Others have discussed similar processes, some capable of longer length bers (Ref 13). Although only discontinuous bers are fabri- cated, they have unique properties approaching those of single crystal graphite in some cases. Available Formats for Fibers. Commercially available carbon bers are produced by a mul- titude of manufacturers with a wide range of properties and tow sizes. Carbon bers are avail- able in many of the same formats as glass ber. These formats include continuous lament- spooled ber, milled ber, chopped ber, woven fabrics, felts, veils, and chopped ber mattes. Most ber today is spooled, and then processed into other formats in secondary operations. The size of the carbon ber tow bundle can range from 1000 laments (1K) to more than 200K. Generally, aerospace carbon bers are available in bundles of 3K, 6K, 12K, and 24K laments, while most commercial-grade bers are avail- able in 48K or larger lament counts. Composite fabrication equipment, such as lament winders and weaving machines, must be adapted to han- dle the larger cross section of commercial grade ber. Properties and Characteristics of Carbon Fibers Composites made from carbon ber are ve times stronger than grade 1020 steel for struc- tural parts, yet are still ve times lighter. In com- parison to 6061 aluminum, carbon ber com- posites are seven times stronger and two times stiffer, yet 1.5 times lighter. Carbon ber com- posites have fatigue properties superior to all known metals, and, when coupled with the proper resins, carbon ber composites are one of the most corrosion resistant materials available. Certain mesophase-pitch-based carbon bers possess thermal conductivity three times greater than copper. The electrical conductivity of PAN and pitch-based carbon bers is used to dissipate static electricity in a wide variety of computer- related products. They do not melt or soften with heat, allowing them to be used in such high tem- perature applications as rocket nozzles and air- craft brakes. In fact, their strength actually in- creases with temperature in non-oxidizing atmospheres. These unique properties are the re- sult of the ber microstructure, in both the axial and transverse directions. Axial Structure. Envision a single carbon l- ament as a long cylinder with a diameter of ap- proximately 7 lm. Packed within this cylinder are tiny undulating ribbon-like crystallites which are intertwined and oriented more or less parallel to the axis of the cylinder (Ref 1416). The length and straightness of these crystallite rib- bons determines the modulus of the ber. A model of the axial structure of a PAN-based car- bon ber is shown in Fig. 2. On a ner scale, each ribbon-like crystallite is comprised of multiple wrinkled layers. Each layer is made of carbon atoms arranged like chicken wire in a hexagonal structure character- istic of graphite, called a graphene plane. Strong covalent C-C bonds within the layer plane give the potential for high strength and stiffness. Weak van der Waals bonding between the layer planes gives rise to poor shear resistance, but also allows thermal and electrical conductivity. Loose electrons and thermal energy in the form of phonons take advantage of the weak bonding between layer planes and use the inter-plane space as a corridor to travel. The width of the ribbons, the number of graphene layers compris- ing their thickness, and the length of the ribbons help determine the electrical and thermal char- acteristics of the carbon ber, as well as contrib- ute to ber modulus. Typically, larger and more oriented graphene planes result in higher thermal and electrical conductivity. Carbon Fibers / 37 Fig. 3 The preferred orientation of the graphene planes is determined by the heat treatment temperature and the precursor type. Source: Ref 14, 18 Fig. 2 The undulating ribbon structure of the graphene layers for a PAN-based carbon ber with a 400 GPa (600 10 6 psi) modulus. The ribbons at the surface have lower amplitude than in the core. There are about 20 graphene layers in the ribbons in the core and about 30 near the surface. Fig. 5 A 400-GPa (60 10 6 psi) modulus PAN-based ber. Source: Ref 26 Fig. 4 The modulus of a carbon ber is determined by the preferred orientation, microstructure, and elastic constants. The relationship between modulus and preferred orientation for a pitch-based carbon ber is shown. Improving the orientation of the microstruc- ture can also increase lament tensile modulus, thermal conductivity, electrical conductivity, and density. This can be accomplished by plastic de- formation (for example, stretching the ber) and/ or heat treatment. Figure 3 shows x-ray diffrac- tion results relating heat treatment temperature to the degree of preferred orientation of the mi- crostructure (Ref 17, 18). The degree of pre- ferred orientation represents the average angle at which the crystallites lie relative to the ber axis; a zero degree angle means that the crystallites are perfectly aligned with the ber axis. Trans- mission electron microscopy shows that the rib- bons undulate, such that their amplitude is greater than their wavelength. Any reported measurement of preferred orientation is therefore only an average. The data clearly shows im- proved orientation with increasing heat treat- ment temperature. Figure 3 also shows that for heat treatment temperatures above 1600 C (2900 F) the mesophase pitch-based ber will orient more than the PAN ber, a result of larger crystallite sizes that PAN precursors are not able to achieve. The relationship between preferred orientation of the microstructure and modulus is illustrated in Fig. 4. Increased orientation results in increased ber modulus, as expected. Increases in ber tensile modulus can also be obtained by stretching the ber during stabili- zation and carbonization. In this case, mechani- cal rather than thermal energy provides the im- petus for molecular realignment. Transverse Structure. While axial orienta- tion determines modulus, ber strength is deter- mined by the number and size of aws and by the transverse and axial orientation. A variety of transverse textures are possible (Ref 19), includ- ing a common one described as onion skin. In this structure, the graphene layer planes at the ber surface align like the layers of an onion. In the center core region of the ber, the layers are randomly oriented. Most of the microstructural pores and aws are found in either the transition from the skin to the random core region, or in the core region; aws resulting from damage in- duced during precursor or carbon ber process- ing are observed on the surface. Some pitch - bers have very large graphene layers in a at orientation reminiscent of the old Pan-Am Air- lines insignia. Some of the ultra-high modulus bers 900 GPa (130 10 6 psi) have a radial structure like the spokes of a wheel. Unlike the axial structure, the radial structure of the carbon lament depends upon precursor type and processing (Ref 2024). Flaw size and aw density reduce the strength of a carbon ber. However, because the ber is bundled with thousands or millions of other - bers in a composite, the strength is an average effect. Fiber manufacturers control the strength of the overall ber bundle through rigorous pro- cess control. Effect of Structure on Properties. Fibers made from PAN precursors generally exhibit higher tensile and compressive strength, higher strain at failure, and lower modulus as compared to mesophase-pitch-based bers. The structure of PAN-based carbon bers leads to a good bal- ance in properties and is responsible for their dominance in structural applications. Relatively good layer alignment and small crystallite stack heights minimize interlayer shear failure, which improves compressive strengths while maintain- ing good tensile strength (Ref 25). A model of a 400 GPa (58 10 6 psi) PAN-based carbon ber is shown in Fig. 5 (Ref 26). PAN bers used to be categorized into stan- dard modulus, intermediate, and high modulus. New offerings by ber producers have blurred these categories somewhat. The differences be- tween the three categories for bers made from a particular precursor are due to combinations of mechanical stretching, heat treatment, and/or precursor spinning. Distinctions are also made between aerospace and commercial-grade car- bon bers. The difference relates to the type of precursor used; commercial grades use a lower cost, modied textile-type PAN. Polyacryloni- trile chemistry is similar between the two, and differences relate more to processing. General- ized properties for PAN-based bers are pre- sented in Table 1. Larger crystallite size and greater orientation of mesophase-pitch-based bers give them su- perior modulus, thermal conductivity, and lower thermal expansion characteristics as compared to PAN-based bers. Satellite applications make extensive use of pitch-based bers and take ad- vantage of all three properties. Table 2 lists gen- eral properties of mesophase-pitch-based bers. One of the most benecial properties of all carbon bers is their superior fatigue resistance in composites. Unlike glass or aramid bers, car- bon bers do not suffer from stress rupture, and demonstrate complete elastic recovery upon un- loading (Ref 2729). Creep is not observed in carbon bers at temperatures below 2200 C (3990 F) (Ref 30). The carbon content of low-modulus carbon - bers is less than 99%, largely because of retained nitrogen (Ref 31). Increasing carbon contents 38 / Constituent Materials Table 1 Properties of PAN-based carbon bers Commercial, Aerospace Property standard modulus Standard modulus Intermediate modulus High modulus Tensile modulus, GPa (10 6 psi) 228 (33) 220241 (3235) 290297 (4243) 345448 (5065) Tensile strength, MPa (ksi) 380 (550) 34504830 (500700) 34506200 (600900) 34505520 (600800) Elongation at break, % 1.6 1.52.2 1.32.0 0.71.0 Electrical resistivity, lX cm 1650 1650 1450 900 Thermal conductivity, W/m K (Btu/ft h F) 20 (11.6) 20 (11.6) 20 (11.6) 5080 (2946) Coefcient of thermal expansion, axial direction, 10 6 K 0.4 0.4 0.55 0.75 Density, g/cm 3 (lb/in. 3 ) 1.8 (0.065) 1.8 (0.065) 1.8 (0.065) 1.9 (0.069) Carbon content, % 95 95 95 99 Filament diameter, lm 68 68 56 58 Manufacturers Zoltek, Fortal, SGL BPAmoco, Hexcel, Mitsubishi Rayon, Toho, Toray, Tenax, Socar, Formosa and densities are achieved through higher heat treatment temperature, which removes nitrogen and provides greater crystalline perfection. Electrical and thermal conductivity also in- crease with increasing crystalline perfection and purity (Ref 32). The electrical conductivity of carbon bers must be taken into account when processing, since free-oating bers can short out electrical equipment. Dust-proof, gasketed NEMA 12 enclosures (as specied by the Na- tional Electrical Manufacturers Association) are recommended for electrical cabinets, as are cov- ers over electrical outlets (Ref 33). Room temperature coefcients of thermal ex- pansion (CTE) in the axial direction are slightly negative for low modulus carbon bers, and grow increasingly negative for the higher mod- ulus bers. At temperatures above 700 C (1290 F), the axial CTE of all bers turns positive (Ref 34). Composite designers are able to couple the negative CTE of high modulus bers with ap- propriate matrix materials to make composites with a CTE of zero over limited temperature ranges. Interfacial Bonding. Resins and molten met- als do not easily wet carbon bers, due to the relatively inert, non-polar ber surface. Glass - bers depend upon coupling agents to chemically bond with resins; carbon bers never achieve strong bonds. Instead, carbon ber depends upon a combination of mechanical and weak chemical bonding with the matrix material. Surface treat- ments used by carbon ber manufacturers pop- ulate the ber surface with active chemical groups such as hydroxyls, carboxyls, and car- bonyls (Ref 35). These form bridges between the ber and resin, and depend upon the number of bonds rather than the strength of the bonds to achieve a strong interface. Reactivity with Other Compounds. As an inorganic material, carbon bers are not affected by moisture, atmosphere, solvents, bases, and weak acids at room temperature (Ref 36). How- ever, oxidation becomes a problem at elevated temperatures. For low-modulus PAN-based - bers and high-modulus PAN- or pitch-based - bers, the threshold for oxidation for extended op- erating times is 350 C (660 F) or 450 C (840 F), respectively (Ref 37). Impurities tend to cat- alyze oxidation at these low temperatures and somewhat improved oxidation resistance can be expected with higher-purity bers (Ref 38). Typical Applications of Carbon Fibers Carbon ber usage is growing in a variety of applications, including aerospace, sporting goods, and a variety of commercial/industrial ap- plications. Growth is fastest in the commercial/ industrial applications. In many instances, car- bon composites have displaced metal parts, despite being more expensive on a direct-re- placement purchased cost basis. Where success- ful, carbon composites have lowered total sys- tem costs through reduced maintenance, faster processing speeds, and improved reliability. Many new uses under development are enabling, meaning applications that were not practical with metal or other materials are now possible with carbon composites. Aerospace. Perhaps nowhere is the need to save weight greater than in the aerospace indus- try. Early growth of the carbon ber industry was driven almost exclusively by the desire for higher performance aircraft made possible with carbon ber composites. Today, carbon ber is used on aircraft for primary and secondary struc- tures. Use is growing, having already established a strong track record in primary structures on military aircraft. All of these applications use carbon ber for its high specic strength and specic stiffness. Fiber formats used include pre- preg for layup processes and fabrics for resin transfer molding and similar processes. Satellites incorporate very high modulus pitch-based carbon bers, partly for the high stiffness-to-weight ratios and partly for their negative axial coefcient of thermal expansion. Sporting Goods. Golf club shafts are pres- ently the largest sporting goods application for carbon bers. Lighter weight and higher stiffness shafts, made possible with carbon ber, allow club manufacturers to place more weight in the clubhead, which increases club head speed for improved distance. Most golf shaft manufactur- ing today is done with unidirectional prepregged sheets of carbon ber in a roll wrapping opera- tion. Some shafts are lament wound. Carbon ber shing rods are favored by sh- erman for their lightweight and sensitive touch. The rods are manufactured via a roll-wrapping process similar to golf shafts, using unidirec- tional prepreg. Most racquets for tennis, rac- quetball, and squash are made from prepregged carbon ber that is sheeted, wrapped around a bladder, and cured. Carbon composite arrows are fabricated by either of two processes: pultrusion or roll wrapping. Skis and bicycle components tend to use fabrics made from carbon ber. Commercial and Industrial Applications. Large volumes of milled and chopped carbon - ber are used to impart static dissipating proper- ties to trays for processing semiconductors, and for computer printer and copier machine parts. Parts are injection molded from thermoplastics that have been pre-blended with carbon ber in a compounding extruder. The carbon ber is used for its electrical conductivity and ability to Table 2 Properties of mesophase pitch-based carbon bers Property Low modulus High modulus Ultra-high modulus Tensile modulus, GPa (10 6 psi) 170241 (2535) 380620 (5590) 690965 (100140) Tensile strength, MPa (ksi) 13803100 (200450) 19002750 (275400) 2410 (350) Elongation at break, % 0.9 0.5 0.40.27 Electrical resistivity, lX cm 1300 900 220130 Thermal conductivity, W/m K (Btu/ft h F) . . . . . . 4001100 (230635) Coefcient of thermal expansion in axial direction, 10 6 K . . . 0.9 1.6 Density, g/cm 3 (lb/in. 3 ) 1.9 (0.069) 2.0 (0.072) 2.2 (0.079) Carbon content, % 97 99 99 Filament diameter, lm 11 11 10 Manufacturers BPAmoco, Mitsubishi Kasei BPAmoco Carbon Fibers / 39 provide lightweight reinforcement to thermo- plastics. Carbon ber drive shafts and couplings have replaced steel shafts for cooling towers and many other torque-transmitting applications. Properties that favor carbon composites include corrosion resistance, light weight, and high stiff- ness, which reduces vibration. Filament winding processes are used to fabricate the shafts and in- corporate ber into various angles tailored for the torque and vibrational characteristics re- quired of the application. The desire for faster processing in the paper- making and lm casting industry has encouraged growth of carbon composite rollers, which spin faster and have less deection than steel rollers. Roller diameters up to one meter are now rou- tinely fabricated with carbon bers on automated lament winding machines. Speed and precision are also drivers for weav- ing machine components, such as rapiers, that are made from pultruded carbon composite shapes. Injection of liquids into oil wells to stimulate production is currently being performed with spoolable carbon composite pipe. The pipe is made in a continuous process whereby a ther- moplastic liner is pulled through multiple sets of rotating creels containing carbon ber spools. The ber is wetted with resin and wrapped onto the liner, which serves as the mandrel. The tube is cured in-line, and spooled at the other end. Although spoolable carbon composite pipe is more expensive than spoolable steel pipe, its us- age is increasing because of superior fatigue per- formance, which results in improved reliability. Stress corrosion during unspooling and respool- ing is responsible for premature failure of steel spoolable pipe. Depletion of shallow water oil elds and the move into deeper water has raised oil company interest in carbon composites. Development pro- grams are underway to moor large oil platforms to the ocean bottom via tethers constructed from pultruded carbon ber rods. Carbon ber tethers are the leading contender for use in water depths beyond 1500 m (5000 ft); this shift is based on its lightweight and high stiffness, which mini- mize the natural frequency of the platform due to wave motion. Steel tethers used in shallower depths are impractical in deeper water, because they cannot support their own weight hanging from the platform. Pultrusion companies that are eyeing the tether application are also pursuing carbon com- posite tendons for pre- and poststressing of pre- cast concrete. Unlike glass ber, carbon com- posite rods are inert to alkaline attack and corrosion and satisfy the increased useful life re- quirement imposed by many municipalities for infrastructure projects. Another pultrusion appli- cation, carbon composite rebar, is being devel- oped for use along the waterfront to combat the high costs of corrosion induced structural dam- age. Seismic retrotting of bridge columns and walls has been extensively performed in Japan with sheets of carbon ber wallpaper or fabrics that are saturated with resin and applied to the concrete structure. The high stiffness of the car- bon minimizes movement of the concrete and the inertness to corrosion insures long term protec- tion. The electrical properties of carbon ber and the ability to congure the material into a semi- permeable membrane with dened mass trans- port properties make carbon the material of choice as the electrode in polymer electrolyte fuel cells to power next generation engines. Anticipated Developments in Carbon Fibers Much of the effort expended for carbon bers today is directed at cost reduction. It appears that the prospects for cost reduction have stimulated interest in many new applications. Certainly, as prices come down, opportunities for new appli- cations grow. Future funding and technology development for carbon bers will most likely be directed to- wards application development, a trend experi- enced in the glass ber industry. Areas of op- portunity include lowering cost and improving speed of manufacturing processes. Education and familiarity with composite ma- terials are increasing, but are still well belowthat of metals. We can expect the demand for carbon bers to grow in large steps as more engineers learn how to design with carbon bers. Property standardization is another expected trend. Glass ber is easy for a designer to design with, since E-glass and S-glass are standards by which many suppliers produce. Carbon ber suppliers have many grades to choose from, with little commonality among producers. As large applications for carbon ber develop, customers will demand standardization among carbon ber producers. REFERENCES 1. T. Edison, U.S. Patent 223,898, 1880 2. R. Bacon and M.M. Tang, Carbonization of Cellulose Fibers I, Carbon, Vol 2, 1964, p 211 3. R. Bacon and C.T. Moses, High-Perfor- mance PolymersTheir Origin and Devel- opment, R.B. Seymour and G.S. Kirshen- baum, Ed., Elseveir, 1986, p 341 4. W. Schimpf, Advanced Fiber Technologies, personal communication, 2000 5. J.B. Donnet and R.C. Bansal, Carbon Fi- bers, 2nd ed., Marcel Dekker, 1990 6. Zoltek Corporation 1994 Annual Report, St. Louis, 1995 7. Zoltek Corporation, unpublished data, 2000 8. K. Shariq, E. Anderson, and M. Yamaki, Carbon Fibers, Chemical Economics Handbook Market Research Report, SRI In- ternational, Menlo Park, CA, July 1999 9. J.B. Donnet and R.C. Bansal, Carbon Fi- bers, 2nd ed., Marcel Dekker, 1990, p 55 10. J.D. Brooks and G.H. Taylor, The Formation of Graphitizing Carbons from the Liquid Phase, Carbon, Vol 3, 1965, p 185193 11. R.P. Krock, D. Carolos, and D.C. Boyer, Versatility of Short Pitch-Based Carbon Fi- bers in Cost Efcient Composites, 42nd Conf. of Composites Institute, SPI, Feb 1987 12. A. Oberlin, M. Endo, and T. Koyama, Fil- amentous Growth of Carbon Through Ben- zene Decomposition, J. Cryst. Growth, Vol 32, 1976, p 335 13. G.G. Tibbetts, Carbon Fiber Filaments and Composites, J.L. Figueiredo et al. Ed., Klu- wer Academic Publishers, 1990, p 7394 14. G.D. DAbate and R.J. Diefendorf, The Ef- fect of Heat on the Structure and Properties of Mesophase Precursor Carbon Fibers, Proc. of the 17th Biennial Conf. on Carbon, American Carbon Society, 1985, p 390 15. R. Perret and W. Ruland, The Microstruc- ture of PAN-Based Carbon Fibers, J. Appl. Crystallogr., Vol 3, 1970, p 525 16. S.C. Bennett and D.J. Johnson, Structural Characterization of a High Modulus Carbon Fibre by High-Resolution Electron Micros- copy and Electron Diffraction, Carbon, Vol 14, 1976, p 177 17. G.D. DAbate and R.J. Diefendorf, The Ef- fect of Heat on the Structure and Properties of Mesopause Precursor Carbon Fibers, Proc. of the 17th Biennial Conf. on Carbon, American Carbon Society, 1985 18. C.W. LeMaistre and R.J. Diefendorf, The Origin of Structure in Carbonized PAN Fi- bers, SAMPE Q., Vol 4, 1973, p 1 19. D.D. Edie and E.G. Soner, Carbon-Carbon Materials and Composites, J.D. Buckley and D.D. Edie, Ed., Noyes Publications, 1993, p 50 20. C.W. LeMaistre and R.J. Diefendorf, The Origin of Structure in Carbonized PAN Fi- bers, SAMPE Q., Vol 4, 1973 21. R.J. Diefendorf and E.W. Tokarsky, The Relationships of Structure to Properties in Graphite Fibers, Part I, AFML-TR-72-133, Air Force Materials Laboratory, 1971 22. R.J. Diefendorf and E.W. Tokarsky, The Relationships of Structure to Properties in Graphite Fibers, Part II, AFML-TR-72- 133, Air Force Materials Laboratory, 1973 23. R.J. Diefendorf and E.W. Tokarsky, The Relationships of Structure to Properties in Graphite Fibers, Part III, AFML-TR-72- 133, Air Force Materials Laboratory, 1975 24. R.J. Diefendorf and E.W. Tokarsky, The Relationships of Structure to Properties in Graphite Fibers, Part IV, AFML-TR-72- 133, Air Force Materials Laboratory, 1975 25. L. Singer, Overview of Carbon Fiber Tech- nology, Material Technology Center News- letter, Southern Illinois Univ. at Carbondale, Spring 1994 26. E.W. Tokarsky and R.J. Diefendorf, High Performance Carbon Fibers, Polym. Eng. Sci., Vol 15 (No. 3), 1975, p 150 27. R.J. Diefendorf, Clemson University, un- published data 40 / Constituent Materials 28. J. Awerback and H.T. Hahn, Fatigue and Proof Testing of Unidirectional Graphite/ Epoxy Composites, Fatigue of Filamentary Composite Materials, STP 636, Am. Soc. for Testing and Materials, 1977, p 248 29. T.T. Chiao, C.C. Chiao, and R.J. Sherry, Lifetimes of Fiber composites Under Sus- tained Tensile Loading, Proceedings of the 1977 Int. Conf. on Fracture Mechanics and Technology, 1977 30. L.A. Feldman, High Temperature Creep Ef- fects in Carbon Yarns and Composites, Pro- ceedings of the 17th Biennial Conference on Carbon, American Carbon Society, 1985, p 393 31. R.J. Diefendorf, Carbon/Graphite Fibers, Composites, Vol 1, Engineered Materials Handbook, ASM International, 1987, p 51 32. A.A. Bright and L.S. Singer, Electronic and Structural Characteristics of Carbon Fibers from Mesophase Pitch, Proceedings of the 13th Biennial Conference on Car- bon, American Carbon Society, 1977, p 100 33. Zoltek Corporation, technical bulletin, St. Louis, MO, 1999 34. R. J. Diefendorf, Carbon/Graphite Fibers, Composites, Vol 1, Engineered Materials Handbook, ASM International, 1987, p 52 35. W. Schimpf, Advanced Fiber Technologies, person communication, 2000 36. N.C.W. Judd, The Chemical Resistance of Carbon Fibers and a Carbon Fibre/Polyester Composite, Proceedings of the First Int. Conf. on Carbon Fibers, Plastics Institute, 1971, p 258 37. D.W. McKee and V.J. Memeault, Surface Properties of Carbon Fibers, Chemistry and Physics of Carbon, Vol 17, Marcel Dekker, 1981, p 1 38. D.W. McKee and V.J. Memeault, Surface Properties of Carbon Fibers, Chemistry and Physics of Carbon, Vol 17, Marcel Dekker, 1981, p 1