CARBON FIBERS:

OPPORTUNITIES AND CHALLENGES

This is Part I of a two-part discussion of carbon fibers and carbon nanotubes. This article covers carbon fibers, and Part II will cover carbon nanotubes in the October issue. M. Rashid Khan
King Abdullah University of Science & Technology Saudi Arabia

Andrew R. Barron
Richard E. Smalley Institute for Nanoscale Science and Technology, Rice University Houston, Texas
Fig. 1 The Boeing 787 Dreamliner has a carbon fiber composite fuselage for reduced weight and improved fatigue properties.

arbon fiber has been described as a fiber containing at least 90% carbon prepared by the controlled pyrolysis and thermal treatment of selected feedstocks and fibers. The ability to fabricate nanomaterials (often in the form of nanoparticles) with strictly controlled size, shape, and structure, has inspired the application of nanochemistry to numerous fields including catalysis, optics, and electronics. The synthesis of well-defined nanoparticles has resulted in several prominent milestones in the progress of nanoscience, including the discovery of fullerenes and carbon nanotubes. The latter material represents a link between well-established carbon materials and the new field of nanotechnology. The applications of these carbon materials in areas as diverse as construction, transportation, medicine, electronics, and energy suggests that the first technology age of the 21st century will be the carbon age. This article discusses carbon fibers, describing manufacturing methods, properties, and several current and potential applications. Making carbon fibers Carbon fibers are manufactured by the controlled thermal treatment of organic precursors (polyacrylonitrile, pitch, or rayon) in fibrous form. Most carbon fiber is made from polyacrylonitrile (PAN). When PAN is thermally treated in an inert atmosphere at 400 to 600C, the heat causes the cyano repeat units to form rings. At still higher temperatures of 600 to 2000C, hydrogen atoms boil off, the carbon becomes more concentrated, and the compound forms a series of fused pyridine rings. During further heat treatment, nitrogen is expelled and the

rings join together to form ribbons with even greater percentages of carbon. As heat treatment continues, the ribbons become wider and more nitrogen is expelled, leaving ribbons that are almost pure carbon in the graphite form. Bundles of these ribbons can be packed together to form fibers, hence the name carbon fiber. When combined with a matrix material such as epoxy, carbon fibers form an advanced composite material with high strength and elastic modulus and relatively low density. It is this unique combination of properties that makes these materials highly advantageous in many advanced applications. PAN fibers PAN fibers are white with a density of 1.17 g/cm3 and a molecular structure comprised of oriented, long-chain molecules. Stabilization involves stretching and heating the PAN fibers to approximately 200 to 300C in an oxygen-containing atmosphere to further orient and then crosslink the molecules, such that they can survive higher-temperature heat treatment without decomposing. After spinning, stretching of fibers during stabilization and heat treatment helps orient the molecules to develop high tensile modulus and tensile strength. A series of heat-treatments at carbonization temperatures ranging from 1000 to 1500C in an inert atmosphere, result in a material with about 95% carbon content. An additional high heat treatment step is included after carbonization for some very high-modulus fibers. During carbonization, the fibers shrink in diameter and lose approximately 50% in weight. Most manufacturers use an electrolytic oxidation process that creates carboxyl, carbonyl, and hydroxyl groups on the surface for enhanced bonding. A sizing or finish is then applied to minimize handling damage 47

ADVANCED MATERIALS & PROCESSES/SEPTEMBER 2008

PAN PROCESS

PAN fibers

Stretch

Oxidation

Pre-carbonization Carbonization c

PITCH PROCESS

Petroleum Melt spin Oxidation pitch Take up CARBON FIBER

Pre-carbonization Carbonization c

Sizing

Surface treatment

Fig. 2 Schematic diagram of processes for PAN and pitch-based carbon fibers.

crystal phase that develops in regions of long-term ordered molecules favorable to manufacture of highperformance fibers. Without this step, the result is an isotropic carbon fiber with low strength and low modulus of less than 50 GPa. Process details of the final composition and method of spinning mesophase pitches are generally held secret by the manufacturers. Once spun, the stabilization, carbonization, surface treatment, application of sizing, and spooling of pitch-based fibers follow a sequence similar to the manufacture of PAN-based fibers. Actual process parameters, such as temperatures, ramp rates, and time at temperature for stretch and stabilization, are different for pitch than for PAN. Carbon fiber composites Composites made from carbon fiber are five times stronger than steel for structural parts, yet are still five times lighter. In comparison to aluminum, carbon fiber composites are seven times stronger and two times stiffer, yet 1.5 times lighter. Carbon fiber composites have fatigue properties superior to all known metals, and, when coupled with the proper resins, carbon fiber composites are one of the most corrosion resistant materials available. Certain mesophase-pitch-based carbon fibers possess thermal conductivity three times greater than copper. The electrical conductivity of PAN and pitchbased carbon fibers is used to dissipate static electricity in a wide variety of computer related products. They do not melt or soften with heat, enabling such high temperature applications as rocket nozzles and aircraft brakes. In fact, their strength actually increases with temperature in non-oxidizing atmospheres. These unique properties are the result of the fiber microstructure, in both the axial and transverse directions. On a finer scale, each ribbon-like crystallite is comprised of multiple layers. Each layer is made of carbon atoms arranged like chicken wire in a hexagonal structure characteristic 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 comprising their thickness, and the length of the ribbons help determine the electrical and thermal characteristics of the carbon fiber, as well as contribute to fiber modulus. Larger and more oriented
Cyclic stress, MPa Max: 861, Min: 296, Range: 565 Max: 220, Min: 21, Range: 199 Life, cycles 2,000,000 + (No failure) 300,000 (Failure)

during spooling, and to enhance bonding with matrix resins. The fiber is then spooled. Today, some manufacturers use a modified textile-type PAN precursor, and others use an aerospace-type precursor. The textile-type precursor is made on a very large scale in modified acrylic textile fiber plants in tows consisting of 200,000 filaments. The tows are then split into smaller bundles (approximately 48,000 filaments) after carbonization for spooling. Aerospace precursor is made in smaller specialty plants and processed in 3000 to 12,000 filament tows that can be assembled into 24,000 or larger tows after carbonization. Because it is processed in smaller tow sizes, the aerospace-type precursor is less fuzzy, and is favored by the aerospace industry for which it was originally developed. Physical properties can be similar for both types. Manufacturing cost is lower for the textile-type precursor (targeted for industrial applications), due to higher line throughputs, larger economies of scale, and less handling of smaller tow bundles. Greater carbon contents and densities are achieved through higher-temperature heat treatments that remove nitrogen and provide greater crystalline perfection. Electrical and thermal conductivity also increase with increasing crystalline perfection and purity. Pitch-based fibers Petroleum pitch is processed in a complicated way. A simplified figure is shown (Fig. 2). Pitch is a complex mixture of aromatic hydrocarbons, and can be made not only from petroleum, but also from coal tar, asphalt, or PVC. Raw material selection is important to the final fiber properties. Pitches must be processed through a pre-treatment step to develop the required viscosity and molecular weight in preparation for making high-performance carbon fibers. The pre-processed pitch contains a mesophase, a term for a disk-like liquid
Component 250 metric tons (560,00 lb), 54 mm (2 inch) diameter carbon fiber strand with potted termination (extrapolation: 127 mm rope has a strength of 1636 metric tons) X60 steel pipe, 609 mm (24 inch) OD and 20 mm (0.8 inch) wall thickness (1636 metric ton yield load)

Fatigue strength of welded steel pipe Vs. carbon fiber strand with potted termination

48

ADVANCED MATERIALS & PROCESSES/SEPTEMBER 2008

graphene planes result in higher thermal and electrical conductivity. Many transverse textures are possible, including a common one described as onion skin. In this structure, the graphene layer planes at the fiber surface align like the layers of an onion. In the center core region of the fiber, the layers are randomly oriented. Most of the micro structural pores and flaws are found in either the transition from the skin to the random core region, or in the core region; flaws resulting from damage induced during precursor or carbon fiber processing are observed on the surface. Flaw size and flaw density reduce the strength of a carbon fiber. Strength is an average effect because the fiber is bundled with thousands or millions of other fibers in a composite. Fiber manufacturers control the strength of the overall fiber bundle through rigorous process control. Composite applications Carbon fiber composites have often lowered total system costs through reduced maintenance, faster processing speeds, and improved reliability. They are ideally suited to applications where strength, stiffness, lower weight, and outstanding fatigue characteristics are critical requirements. They are also ideal for applications in which high temperature operation and chemical inertness are important. Aerospace: Early growth of the carbon fiber industry was driven almost exclusively by the need for higher performance aircraft made possible with carbon fiber composites. Satellites: Space-based satellites incorporate very high modulus pitch-based carbon fibers, partly for the high stiffness-to-weight ratios, and partly for their negative axial coefficient of thermal expansion. Automotive: Carbon/carbon brakes, liquefied natural gas tankage, specialty auto and truck panels, and drive shafts all are made of carbon fiber-reinforced thermoplastics and thermosets. Applications will expand significantly when carbon fiber prices are reduced below $20 /kg. Sporting goods: Lighter weight and higher stiffness golf shafts allow manufacturers to place more weight in the club head, which increases club head speed for improved distance. Carbon fiber tethers are the leading contender for oil platforms in water depths beyond 5000 ft; this shift is based on its lightweight and high stiffness, which minimize the natural frequency of the platform due to wave motion. Carbon composite rebar is being developed to combat the high costs of corrosion induced structural damage. Carbon fiber fabrics saturated with resin are applied to concrete bridge columns in Japan for seismic protection. The high stiffness of the carbon minimizes movement of the concrete, and the inertness to corrosion insures long term protection. Semi permeable membranes with defined mass transport properties make carbon fibers the material of choice as the electrode in polymer electrolyte fuel cells. Carbon composite rollers spin faster and have less deflection than steel rollers for papermaking and similar industries.
For more information: M. Rashid Khan is with Intellectual Assets & Technology Management, Saudi Aramco, Saudi Arabia; Rashid.Khan.1@aramco.com; Rashkhan@gmail.com. Current affiliation is with King Abdullah University of Science & Technology (KAUST), Saudi Arabia. Andrew R. Barron is Associate Dean of Industry Interactions and Technology Transfer at the Wiess School of Natural Sciences, Rice University, Houston, TX 77005; arb@rice.

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